Partly immobilized ionic liquid electrolyte additives for lithium ion batteries

ABSTRACT

Electrolytes, anodes, lithium ion cells and methods are provided for preventing lithium metallization in lithium ion batteries to enhance their safety. Electrolytes comprise up to 20% ionic liquid additives which form a mobile solid electrolyte interface during charging of the cell and prevent lithium metallization and electrolyte decomposition on the anode while maintaining the lithium ion mobility at a level which enables fast charging of the batteries. Anodes are typically metalloid-based, for example include silicon, germanium, tin and/or aluminum. A surface layer on the anode bonds, at least some of the ionic liquid additive to form an immobilized layer that provides further protection at the interface between the anode and the electrolyte, prevents metallization of lithium on the former and decomposition of the latter.

CROSS REFERENCE TO RELATED APPLICATIONS

This application claims the benefit of U.S. Provisional Patent Application No. 62/319,341, filed Apr. 7, 2016, 62/337,416, filed May 17, 2016, 62/371,874, filed Aug. 8, 2016, 62/401,214, filed Sep. 29, 2016, 62/401,635, filed Sep. 29, 2016, 62/421,290, filed Nov. 13, 2016, 62/426,625, filed Nov. 28, 2016, 62/427,856, filed Nov. 30, 2016, 62/435,783, filed Dec. 18, 2016 and 62/441,458, filed Jan. 2, 2017, all of which are hereby incorporated by reference.

BACKGROUND OF THE INVENTION 1. Technical Field

The present invention relates to the field of lithium ion batteries, and more particularly, to electrolytes for preventing lithium metallization.

2. Discussion of Related Art

With continued success in the portable electronic device market, Li-ion batteries (LIBs) are of increasing interest for applications in electric and hybrid vehicles, surgical tools, and oil and gas drilling, etc., due to their superior energy density and long cycle life. However, current LIBs employ conventional liquid electrolytes based on organic solvents, which poses a safety concern, especially at elevated temperatures. Specifically, the use of carbonate solvents such as ethylene carbonate (EC), dimethyl carbonate (DMC), or diethyl carbonate (DEC) restricts battery operation to less than 60° C. due to their volatile and highly flammable nature. Moreover, when these solvents are used with Li salts, such as lithium hexafluorophosphate (LiPF₆), a resistive film forms on the electrode surface affording poor cycle life. These side reactions become more dominating at higher temperatures as the rate of chemical reaction between the dissolved lithium salt and electrolyte solvent increases.

SUMMARY OF THE INVENTION

The following is a simplified summary providing an initial understanding of the invention. The summary does not necessarily identify key elements nor limit the scope of the invention, but merely serves as an introduction to the following description.

One aspect of the present invention provides a lithium ion cell comprising an anode and an electrolyte comprising at most 20% vol of at least one ionic liquid additive, wherein the anode comprises a surface layer configured to bond at least a portion of the at least one ionic liquid additive.

These, additional, and/or other aspects and/or advantages of the present invention are set forth in the detailed description which follows; possibly inferable from the detailed description; and/or learnable by practice of the present invention.

BRIEF DESCRIPTION OF THE DRAWINGS

For a better understanding of embodiments of the invention and to show how the same may be carried into effect, reference will now be made, purely by way of example, to the accompanying drawings in which like numerals designate corresponding elements or sections throughout.

In the accompanying drawings:

FIG. 1A is a high-level schematic illustration of a metallization process in lithium ion batteries according to the prior art.

FIG. 1B is a high level schematic illustration of various anode configurations, according to some embodiments of the invention.

FIGS. 2A-2D and 3A-3C schematically illustrate at least one electrolyte-buffering zone (mobile solid-electrolyte interface, MSEI) in an electrolyte, according to some embodiments of the invention.

FIG. 3D is a high level schematic illustration of some of the considerations in determining an amount of ionic liquid additive, according to some embodiments of the invention.

FIGS. 4A and 4B are high level schematic illustrations of an immobilized/mobilized SEI (I/MSEI) during charging and discharging, according to some embodiments of the invention.

FIG. 5A is a high level schematic illustration of bonding molecules forming a surface molecular layer on the anode and/or anode active material particles, according to some embodiments of the invention.

FIG. 5B is a high level schematic illustration of non-limiting examples for bonding molecules, according to some embodiments of the invention.

FIG. 6 is a high level schematic illustration of bonding molecules forming a surface molecular layer on the anode and/or anode active material particles, according to some embodiments of the invention.

FIG. 7 is a high level schematic illustration of bonding molecules forming thick surface molecules layer on the anode and/or anode active material particles, according to some embodiments of the invention.

FIGS. 8A and 8B are high level schematic illustrations of a lithium ion cell with the electrolyte during charging, according to some embodiments of the invention.

FIG. 9 is a high level flowchart illustrating a method, according to some embodiments of the invention.

FIGS. 10A and 10B are non-limiting examples which indicate reversible lithiation at the anode when using the ionic liquid additive according to some embodiments of the invention with respect to the prior art.

DETAILED DESCRIPTION OF THE INVENTION

In the following description, various aspects of the present invention are described. For purposes of explanation, specific configurations and details are set forth in order to provide a thorough understanding of the present invention. However, it will also be apparent to one skilled in the art that the present invention may be practiced without the specific details presented herein. Furthermore, well known features may have been omitted or simplified in order not to obscure the present invention. With specific reference to the drawings, it is stressed that the particulars shown are by way of example and for purposes of illustrative discussion of the present invention only, and are presented in the cause of providing what is believed to be the most useful and readily understood description of the principles and conceptual aspects of the invention. In this regard, no attempt is made to show structural details of the invention in more detail than is necessary for a fundamental understanding of the invention, the description taken with the drawings making apparent to those skilled in the art how the several forms of the invention may be embodied in practice.

Before at least one embodiment of the invention is explained in detail, it is to be understood that the invention is not limited in its application to the details of construction and the arrangement of the components set forth in the following description or illustrated in the drawings. The invention is applicable to other embodiments that may be practiced or carried out in various ways as well as to combinations of the disclosed embodiments. Also, it is to be understood that the phraseology and terminology employed herein is for the purpose of description and should not be regarded as limiting.

The following analysis of lithium metallization and dendrite growth in some prior art anodes was used to define a problem which is solved by embodiments of the invention. The present disclosure is however not limited by the disclosed analysis, and is in general not bound by theory.

FIG. 1A is a high-level schematic illustration of a metallization process in lithium ion batteries according to the prior art. Typical lithium ion batteries use graphite anodes 95 which receive lithium ions 91 (passing through a prior art electrolyte 85) in an intercalation process between graphite layers. The maximal capacity of the graphite is limited to approximately one lithium ion for every ca. six carbon atoms and is influenced by the solid-electrolyte interface (SEI) formed between anode 95 and electrolyte 85, typically on the intercalation basal planes (e.g., layers in the graphite material between which the lithium ions intercalate). Such lithium ion batteries typically have low charging and discharging rates due to limiting charge transfer rates and limiting lithium ions diffusion rate into the graphite anode. As shown schematically in illustration 90A in FIG. 1A, under low charging rates, the intercalation rate is higher than the lithium ion accumulation rate, resulting in proper intercalation 96 of lithium ions Li⁺ into graphite anode 95 as L^(˜0i), denoting approximately neutral lithium atoms which receive electrons e⁻ from the graphite and are intercalated in anode 95. The intercalation rate is limited by the Li⁺ supply rate. As the charging rate increases (schematic illustrations 90B, 90C, 90D represent gradually increasing charging rate with respect to illustration 90A), the rate of incoming lithium ions increases, and lithium ions accumulate on the surface (of anode 95 or particles thereof, at the solid-electrolyte interface) as illustrated in 90B, with an accumulation rate that exceeds the intercalation rate of the lithium ions. As a result, reduction 97 of the lithium ions is carried out on the interface in addition to the intercalated lithium ions, as illustrated in 90C, which shows schematically the increasing flow of electrons to the interface without lithium ion intercalation in anode 95. Finally, as lithium ion accumulation and reduction at the interface increase (as illustrated in 90D), lithium metallization at the interface and dendrite growth 99 commence and damage the cell. Additional considerations include volume changes of the graphite electrode material, influences of anode additives, characteristics of the SEI and details of the charging and discharging cycles. Without being bound by theory, FIG. 1A illustrates schematically a probable occurrence on the anode surface during slow 90A and fast 90B-D charging, without the problematic catalytic reaction of the active material with the electrolyte (which complicates the schematically illustrated mechanism). While at low C rate the apparent diffusion to the active material is fast enough to compensate the migration of the lithium ions through the electrolyte—at high C rate charging, the migration through the electrolyte is faster than the apparent active material lithiation, which gives rise to metallization process at the interface. Moreover, without proper protective coating around the active material metalloid, the active material-Li entity is highly reactive toward the electrolyte, giving rise to catalytic reaction which decompose the electrolyte.

Embodiments of the present invention provide efficient and economical methods and mechanisms for preventing lithium metallization in lithium ion batteries (LIBs) and thereby provide improvements and enhancing safety in this technological field. It is suggested to use ionic liquids as an additive to prior art organic electrolyte 85 at low concentrations (e.g., up to ˜20% v/v) in order, e.g., to create a mobilized SEI (MSEI) zone during charging and dis-charging. These ionic liquids may be selected to be non-reactive or to have a very low reactivity toward metallic lithium. A surface layer on the anode material particles bonds (e.g., electrostatically and/or ionically) at least some of the ionic liquid additive to form an immobilized layer that provides further protection at the interface between the anode and the electrolyte, prevents metallization of lithium on the anode and decomposition of the electrolyte.

Electrolytes, anodes, lithium ion cells and methods are provided for preventing lithium metallization in lithium ion batteries to enhance their safety. Electrolytes comprise up to 20% ionic liquid additives which form a mobile solid electrolyte interface (mobile SEI or MSEI) during charging of the cell and prevent lithium metallization and electrolyte decomposition on the anode while maintaining the lithium ion mobility at a level which enables fast charging of the batteries. Anodes used with the present invention may be metalloid-based, for example the anodes may include silicon, germanium, tin and/or aluminum (as used herein, “metalloid-based”). However, the invention may also be applied for cells having graphite-based anodes.

In certain embodiments, a surface layer on the anode material particles may be applied to bond (e.g., electrostatically and/or ionically) at least some of the ionic liquid additive to form an immobilized layer (I/MSEI) that may provide further protection at the interface between the anode and the electrolyte, may prevent metallization of lithium on the former and decomposition of the latter. It is emphasizes that MSEI and/or I/MSEI may be created independently of each other, and possibly in addition to other types of SEI which may be formed in or at the surface of the anode material particles.

Advantageously, some embodiments of the invention provide alternative electrolytes with superior thermal and chemical stability, which expand the use of LIBs to a wider working temperature range without compromising the electrochemical performance. Moreover, some embodiments of the invention enable use of high energy metalloids and metals as anode active material, including C (graphite), as well as Si, Ge, Sn, Al, as disclosed e.g., in U.S. Pat. No. 9,472,804, filed on Nov. 12, 2015 and U.S. Pat. No. 9,406,927, filed on Feb. 4, 2016; and in U.S. application Ser. No. 14/813,499 filed on Jul. 30, 2015 which are incorporated herein by reference in their entirety. Advantageously, disclosed MSEI may prevent breaking and/or provide a healing mechanism for damage to fragile SEI layer(s) due to expansion and/or shrinkage of the anode. Moreover, disclosed embodiments reduce, to at least a partial extent during the cycle life of the LIB, decomposition of the electrolyte solvent at the interface with the metalloid, which may act as a catalytic surface due to lithium metal species at the interface such as lithium silicide (Li—Si).

FIG. 1B is a high level schematic illustration of various anode configurations, according to some embodiments of the invention. FIG. 1B illustrates schematically, in a non-limiting manner, a surface of anode 100, which may comprise anode active material particles 110 (e.g., particles of metalloids such as silicon, germanium and/or tin, and/or of aluminum, see below for more details, possibly composite particles 110B) at different sizes (e.g., in the order of magnitude of 100 nm, and/or possible in the order of magnitude of 10 nm or 1μ)—for receiving lithiated lithium during charging and releasing lithium ions during discharging. Anodes 100 may further comprise binder(s) and additive(s) 108 as well as optionally coatings 106 (e.g., conductive polymers, lithium polymers, etc.). Active material particles 110 may be pre-coated by one or more coatings 106 (e.g., by conductive polymers, lithium polymers, etc.), have borate and/or phosphate salt(s) 102A bond to their surface (possibly forming e.g., B₂O₃, P₂O₅ etc.), bonding molecules 116 (illustrated schematically and disclosed in detail below) which may interact with electrolyte 105 (and/or ionic liquid additives thereto, see below) and/or various nanoparticles 102 (e.g., B₄C, WC, VC, TiN), may be attached thereto in anode preparation processes 103 such as ball milling (see, e.g., U.S. Pat. No. 9,406,927, which is incorporated herein by reference in its entirety), slurry formation, spreading of the slurry and drying the spread slurry. For example, anode preparation processes 103 may comprise mixing additive(s) 108 such as e.g., binder(s) (e.g., polyvinylidene fluoride, PVDF, styrene butadiene rubber, SBR, or any other binder), plasticizer(s) and/or conductive filler(s) with a solvent such as water or organic solvent(s) (in which the anode materials have limited solubility) to make an anode slurry which is then dried, consolidated and is positioned in contact with a current collector (e.g., a metal, such as aluminum or copper). Details for some of these possible configurations are disclosed below.

Certain embodiments comprise anode material particles 110 comprising any of silicon active material, germanium active material and/or tin active material, possibly further comprising carbon material, boron and/or tungsten. As non-limiting examples, anode material particles 110 may comprise 5-50 weight % Si, 2-25 weight % B and/or 5-25 weight % W, and 0.01-15 weight % C (e.g., as carbon nanotubes, CNT); anode material particles 110 may comprise 5-80 weight % Ge, 2-20 weight % B and/or 5-20 weight % W, and 0.05-5 weight % C (e.g., as carbon nanotubes, CNT); anode material particles 110 may comprise 5-80 weight % Sn, 2-20 weight % B and/or 5-20 weight % W, and 0.5-5 weight % C (e.g., as carbon nanotubes, CNT); anode material particles 110 may comprise mixtures of Si, Ge and Sn, e.g., at weight ratios of any of at least 4:1 (Ge:Si), at least 4:1 (Sn:Si) or at least 4:1 (Sn+Ge):Si; anode material particles 110 may comprise aluminum and/or any of zinc, cadmium and/or lead, possibly with additions of borate and/or phosphate salt(s) as disclosed below.

Certain embodiments comprise anode material particles 110 comprising nanoparticles 102 attached thereto, such as any of B₄C, WC, VC and TiN, possibly having a particle size range of 10-50 nm and providing 5-25 weight % of modified anode material particles 110A. Nanoparticles 102 may be configured to form in modified anode material particles 110A compounds such as Li₂B₄O₇ (lithium tetra-borate salt, e.g., via 4Li+7MeO+2B₄C→2Li₂B₄O₇+C+7Me, not balanced with respect to C and O, with Me denoting active material such as Si, Ge, Sn etc.) or equivalent compounds from e.g., WC, VC, TiN, which have higher affinity to oxygen than the anode active material.

Certain embodiments comprise anode material particles 110 comprising coatings(s) 104 of any of lithium polymers, conductive polymers and/or hydrophobic polymers, such as e.g., any of lithium polyphosphate (Li_((n))PP or LiPP), lithium poly-acrylic acid (Li_((n))PAA or LiPAA), lithium carboxyl methyl cellulose (Li_((n))CMC or LiCMC), lithium alginate (Li_((n))Alg or LiAlg) and combinations thereof, with (n) denoting multiple attached Li; polyaniline or substituted polyaniline, polypyrroles or substituted polypyrroles and so forth.

Any of anode material particles 110, 110A, 110B may be coated by thin films (e.g., 1-50 nm, or 2-10 nm thick) of carbon (e.g., amorphous carbon, graphite, graphene, etc.) and/or transition metal oxide(s) (e.g., Al₂O₃, B₂O₃, TiO₂, ZrO₂, MnO etc.)

In certain embodiments, borate and/or phosphate salt(s) 102A may comprise borate salts such as lithium bis(oxalato)borate (LiBOB, LiB(C₂O₄)₂), lithium difluoro(oxalato)borate (LiFOB, LiBF₂(C₂O₄)), lithium tetraborate (LiB₄O₇), lithium bis(malonato)borate (LiBMB), lithium bis(trifluoromethanesulfonylimide) (LiTFSI), or any other compound which may lead to formation of borate salts (B₂O₃) on anode active material particles 110, including in certain embodiments B₄C nanoparticles 102.

In certain embodiments, borate and/or phosphate salt(s) 102A may comprise phosphate salts such as lithium phosphate (LiPO₄), lithium pyrophosphate (LiP₂O₇), lithium tripolyphosphate (LiP₃O₁₀) or any other compound which may lead to formation of phosphate salts (P₂O₅) on anode active material particles 110.

Certain embodiments comprise composite anode material particles 110B which may be configured as core shell particles (e.g., the shell being provided by any of coating(s) 104 and possible modifications presented above). The different configurations are illustrated schematically in different regions of the anode surface, yet embodiments may comprise any combinations of these configurations as well as any extent of anode surface with any of the disclosed configurations. Anode(s) 100 may then be integrated in cells 150 which may be part of lithium ion batteries, together with corresponding cathode(s) 87, electrolyte 105 and separator 86, as well as other battery components (e.g., current collectors, electrolyte additives—see below, battery pouch, contacts, and so forth).

Anode material particles 110, 110A, 110B, anodes 100 and cells 150 may be configured according to the disclosed principles to enable high charging and/or discharging rates, ranging from 3-10 C-rate, 10-100 C-rate or even above 100 C, e.g., 5 C, 10 C, 15 C, 30 C or more. It is noted that the term C-rate is a measure of charging and/or discharging of cell/battery capacity, e.g., with 1 C denoting charging and/or discharging the cell in an hour, and XC (e.g., 5 C, 10 C, 50 C etc.) denoting charging and/or discharging the cell in 1/X of an hour—with respect to a given capacity of the cell.

Examples for electrolyte 105 may comprise liquid electrolytes such as ethylene carbonate, diethyl carbonate, propylene carbonate, vinylene carbonate, fluoroethylene carbonate (FEC), and combinations thereof and/or solid electrolytes such as polymeric electrolytes such as polyethylene oxide, fluorine-containing polymers and copolymers (e.g., polytetrafluoroethylene), and combinations thereof. Electrolyte 105 may comprise lithium electrolyte salt(s) such as LiPF₆, LiBF₄, lithium bis(oxalato)borate, LiN(CF₃SO₂)₂, LiN(C₂F₅SO₂)₂, LiAsF₆, LiC(CF₃SO₂)₃, LiClO₄, LiTFSI, LiB(C₂O₄)₂, LiBF₂(C₂O₄)), tris(trimethylsilyl)phosphite (TMSP), lithium 4,5-dicyano-2-(trifluoromethyl)imidazolide (LiTDI), and combinations thereof. Ionic liquid(s) 135 may be added to electrolyte 105 as disclosed below. Cathode(s) 87 may comprise various compositions, such as LiCoO₂, LiCo_(0.33)Mn_(0.33)Ni_(0.33)O₂, LiMn₂O₄, LiFePO₄ and/or combinations thereof. Separator(s) 87 may comprise various materials, such as polyethylene (PE), polypropylene (PP) or other appropriate materials.

FIGS. 2A-2D and 3A-3C schematically illustrate at least one electrolyte-buffering zone 130 (MSEI) in an electrolyte 105, according to some embodiments of the invention. Electrolyte-buffering zone(s) 130 may be formed by an ionic liquid additive 135 (one or more salt(s) which are liquid below 100° C., or even at room temperature or at lower temperatures—sometimes called “fused salts”) and is illustrated schematically as an accumulation of anions 131 and cations 132, which provides separation between organic electrolyte 85 (as main component of electrolyte 105) and anode 100 (illustrated e.g., with respect to anode material particle 110) and may be configured to further regulate lithium ion movement from electrolyte 105 to anode 100 (illustrated e.g., with respect to anode material particles 110). It is noted that shapes and sizes of anions 131 and cations 132 are used for illustration purposes, anions 131 and cations 132 may have various relative sizes and shapes, depending on the specific ionic liquid(s) which are selected as ionic liquid additive 135. For example, anions 131 and/or cations 132 may be relatively large, e.g., larger than lithium ions 91 and/or significantly larger than lithium ions 91 (e.g., larger than lithium ions by at least 10%, 25%, 50% or more, possibly by at least 100%, 200%, 500% or even more, in either volume or radius) to establish a gradient in physical and/or chemical characteristics in region 130 and possibly provide an interphase transition between electrolyte 105 and anode 100 (illustrated e.g., with respect to anode material particles 110) that enhances the stabilization of transition region and prevents lithium ion accumulation and/or metallization and dendrite growth. Anions 131 may be selected to provide negative electric charge in the region of lithium ions 91 moving towards anode 100 (illustrated e.g., with respect to anode material particles 110), which somewhat, yet not fully, reduces the positive charge of lithium ions 91 to δ+ (e.g., by physical proximity, such as through, e.g., electrostatic and/or ionic interactions, and not by a chemical bond). The relative sizes of anions 131 and cations 132 may vary—anions 131 and cations 132 may have a similar size or one of anions 131 and cations 132 may be larger than the other. Mixtures of different ionic liquid additives 135 may have different size relations between their anions 131 and cations 132.

In certain embodiments, electrolyte 105 may comprise ionic liquid additive 135 (e.g., at 20%, 10%, 5%, 2%, 1% v/v or any other volume part smaller than 20%), added to prior art electrolyte 85, which is selected to at least partially provide anions 131 and/or cations 132 to build electrolyte-buffering zone(s) 130. For example, ionic liquid additive 135 may comprise acidic groups which are selected to be anionic in the environment of lithium ions 91. Anions 131 and/or cations 132 may be relatively large to form a barrier which reduces the approaching speed of lithium ions 91 and which locally increases the resistance of electrolyte-buffering zone(s) 130 to lithium ions 91 to prevent or attenuate accumulation of lithium ions 91 at the surface of anode 100 (illustrated e.g., with respect to anode material particles 110).

Ionic liquid additive 135 may be selected to be not reactive in the cell, not to be reactive with lithium metal (e.g., not decompose in the presence of lithium metal) and not to intercalate with active material 110 of anode 100. The ionic strength and lithium ion mobility may be selected to appropriate values and the ionic conductivity may be controlled in a better way than a single component electrolyte 85. Moreover, ionic liquid additive 135 may be selected to have large volume anions 131 and cations 132 (illustrated schematically in FIGS. 2A-C). Advantageously, using ionic liquid additive 135 in the cell overcomes a prior art need to balance the risk of lithium metallization (requiring low lithium accumulation concentration at the anode surface) with the ability to fast charge the battery over a large number of cycles (requiring high lithium conductivity and mobility).

FIG. 2A illustrates schematically the situation prior to application of an electrical field in the vicinity of anode 100 (illustrated e.g., with respect to anode material particles 110) and FIGS. 2B and 2D illustrate schematically the situation during application of an electrical field in the vicinity of anode 100 (e.g., anode material particles 110). In the former case (FIG. 2A), the dispersion of anions 131 and cations 132 of ionic liquid additive 135 in electrolyte 105 may be essentially homogenous while in the latter case (FIGS. 2B, 2D, e.g., during charging of the cell), anions 131 and cations 132 of ionic liquid additive 135 accumulate in zone 130 in electrolyte 105 which is adjacent to the active material surface of anode 100. Without being bound to theory, anions 131 and cations 132 are held adjacent to anode 100 by electrostatic forces, without reacting chemically with the active material of anode 100. Electrolyte-buffering zone(s) 130 may vary in the degree to which anions 131 and cations 132 are ordered, typically the degree of order decreases with increasing distance from the anode surface as the electrostatic forces become weaker.

FIG. 2C is a high level schematic illustration of non-limiting examples for ion sizes and shapes of ionic liquid additive 135, according to some embodiments of the invention. Cations 132 and anions 131 may have various sizes and shapes, e.g., cations 132 may be larger than anions 131, cations 132 may be smaller than anions 131, cations 132 may be about the same size as anions 131, and/or combinations of cations 132 and anions 131 with different size relations may be used together as ionic liquid additive 135. Cations 132 may be elongated or spherical, anions 131 may be elongated or spherical and/or combinations of cations 132 and anions 131 with different shapes may be used together as ionic liquid additive 135. At least one of cations 132 and anions 131 may be larger than lithium ions 91, as illustrated schematically in FIG. 2C. Any of these combinations may be used in any of the disclosed embodiments, and the specific shapes and sizes of cations 132 and anions 131 illustrated in FIGS. 2A, 2B, 2D, 3B and 3C may be replaced with any of the shapes and sizes illustrated in FIG. 2C, and are non-limiting.

FIG. 2D illustrates schematically possible different thicknesses of electrolyte-buffering zone(s) 130 and the spreading of the charge with distance from anode 100 and/or anode material 110. For example, electrolyte-buffering zone(s), MSEI 130, may comprise 1, 2, 4 or more layers of cations 132 and anions 131, depending on electrolyte composition, types of ionic liquid additive 135, sizes of ions, level of charge etc.

Ionic liquid additive 135 may be selected to enable lithium ion transport therethrough while partly reducing the lithium ions and keep them in a partly charged form Li^(δ+) in zone 130.

FIG. 3A schematically illustrates at least one electrolyte-buffering zone 130 (MSEI) in an electrolyte 105, which is configured to provide a mobility and charge gradient 120 (indicated schematically by the tapered arrows) having surrounding electric charge 136 (illustrated schematically as a non-specific symbol), according to some embodiments of the invention. Mobility and charge gradient 120 reduces and slows lithium ions 91 entering zone 130 in a gradual manner (indicated schematically by Li^(δ+), with the partial charge of the lithium ions changing gradually within zone 130) until they reach intercalation in anode 100. Gradient 120 enables modification of the interface (the area where the two immiscible phase surfaces of anode and electrolyte are coming in contact with each other) into an interphase region 130 having a gradual change of parameters which gradually reduces the activation energy of the reduction reaction of the lithium ions, and further prevents metallization of lithium and dendrite growth. MSEI zone 130 helps smooth the lithium ion transport into the active material for full reduction and intercalation (to Li^(˜0i)). The resulting ionic liquid layer 130 reduces the probability of both lithium metallization and decomposition of the organic solvent (electrolyte 85) at the metalloid-lithium surface. Once the electrical field stops (e.g., at the end or interruption of the charging), ionic liquid 135 may slowly diffuse to form homogenous electrolyte 105. It is explicitly noted, however, that ionic liquid additive 135 may be used in cells having metalloid-based and/or graphite-based anodes (either possibly coated and/or pre-coated).

FIG. 3B schematically illustrates at least one electrolyte-buffering zone 130 (MSEI) in an electrolyte 105, which is configured to fill possible cracks 114 appearing in a surface 112 of anode, e.g., due to cracking of a surface layer 115 (which may be e.g., a SEI, a coating and/or an anode buffering zone, e.g., as disclosed in the applications cited above) upon expansion and contraction of anode 100, according to some embodiments of the invention.

Under various configurations of anodes 100, cracks may appear in surface layer 115 of anode, which may comprise or support a SEI (which may be brittle), a coating and/or a buffering zone. Such cracks may enable renewed contact between the anode material and/or metal lithium and electrolyte 85, or increase the surface area available for such contact—causing further electrolyte decomposition and possible sites for lithium metallization. Ionic liquid additive 135 may be configured to fill in such cracks 114 (illustrated schematically in FIG. 3B) once an electric field is applied, or possibly also after the electric field is applied, to reduce the extent of, or prevent, cracks 114 from enhancing electrolyte decomposition and lithium metallization. Anode 100 may be coated and/or pre-coated by a full or partial coating (e.g., a polymer coating, a nanoparticles coating, etc., e.g., on as at least part of surface layer 115, e.g., as disclosed in the applications cited above, and see FIG. 1B), which may be applied before and/or after anode formation (pre- and/or post-coating). Ionic liquid additive 135 may be configured to fill in cracks or uncoated surface areas as explained above, including possible exposed surfaces in the coating resulting from the expansion and contraction during cell cycles (see also FIG. 3C).

FIG. 3C schematically illustrates the ability of mobilized SEI (MSEI) layer 130 to rearrange and maintain itself as electrolyte-buffering zone(s) 130 upon expansion and contraction of anode 100, according to some embodiments of the invention. Expansion 100A and contraction 100B are illustrated schematically by the respective arrows, the indication of amount of intercalated lithium (denoted Li^(˜0i)) which correspond to (partly) discharged state 101A and (partly) charged state 101B, the schematically illustrated movement of anode surface 112 from 112A to 112B and expansion of surface layer 115 from 115A to 115B. Ionic liquid additive 135, being a liquid, accommodates itself easily (illustrated schematically by MSEI layers 130A, 130B) upon expansion 100A and contraction 100B by re-arrangement of cations 132 and anions 131 (from schematically illustrated arrangement 132A, 131A to 132B, 131B, corresponding to MSEIs 130A, 130B).

Without being bound by theory, the mechanism of MSEI formation may be both concentration and kinetically controlled, e.g., the more ionic liquid additive 135 is separated from electrolyte 105, the faster mobile SEI layer 130 forms; while an increase of the concentration of ionic liquid additive 135 may reduce the ionic mobility through MSEI 130. The concentration of ionic liquid additive 135 may thus be selected to balance reduced ionic mobility by higher concentration with possible electrolyte decomposition on the active material-electrolyte interface which may be enabled by too low concentrations of ionic liquid additive 135 (which forms MSEI 130 too slowly). Moreover, using ionic liquid additive 135 may maintain or enhance the ionic strength, without compromising the ionic mobility by increasing the ionic resistance, by enabling a reduction of the lithium salt (e.g., LiPF₆) concentration, which also further reduces the probability for metallization.

In embodiments, the ionic liquid additive contains a charged nitrogen atom. Non-limiting examples of ionic liquid additives 135 include, without limitation, any of the following and their combinations: 1-butyl-1-methylpyrrolidinium as cation 132 and bis(trifluoromethanesulfonyl)imide as anion 131 (melting point −6° C.); 1-butyl-3-methylimidazolium as cation 132 and bis(trifluoromethanesulfonyl)imide as anion 131 (melting point −4° C.); 1-butyl-3-methylimidazolium as cation 132 and bis(fluorosulfonyl)imide as anion 131 (melting point −13° C.); N,N-Diethyl-N-methyl-N-propylammonium as cation 132 and bis(fluorosulfonyl)imide as anion 131; and N-propyl-N-methylpiperidinium as cation 132 and bis(trifluoromethanesulfonyl)imide as anion 131. Certain embodiments comprise ionic liquids which are derived from these combinations, i.e., having various substituents. As illustrated in the examples above, ionic liquid additives 135 may be based on sulfonylimides as anions 131 and on piperidinium derivatives as cations 132, referred to below as ionic liquids based on sulfonylimides and piperidinium derivatives.

Advantageously, certain embodiments use, as ionic liquid additives 135, ionic liquids having a negligible vapor pressure and which are liquid at room temperature, a wide electrochemical potential window (e.g., up to 5.0 V in ionic liquids based on sulfonylimides and piperidinium derivatives), and structural stability across a large temperature range (e.g., up to 385° C. in ionic liquids based on sulfonylimides and piperidinium derivatives). For example, the ionic liquids may have melting temperatures of 10-20° C., 0-10° C., or possibly even <0° C., e.g., 0-−4° C., −4°-−13° C., or even lower, e.g., below −20° C., having melting points down to −40° C., as non-limiting examples. The lithium ion conductivity in certain ionic liquids based on sulfonylimides and piperidinium derivatives at room temperature may be, for example, between 1-20 mS/cm (at 20° C.), in some embodiments, between 1.4-15.4 mS/cm (at 20° C.), wherein exact values can be provided according to requirements.

The use of ionic liquids as additive 135 solves prior art problems in attempting to use ionic liquids as electrolytes 85, such as their high viscosity and low Li-ion conductivity at room temperature and reduced cathodic stability. Their use as additives 135 (e.g., up to 20% vol of electrolyte 105, the rest comprising electrolyte 85) mitigates their prior art disadvantages and utilizes their advantageous property exactly where needed, e.g., at the anode-electrolyte interface. Moreover, the use of ionic liquids based on sulfonylimides and piperidinium derivatives with C (e.g., graphite), or metalloid (e.g., Si, Sn, Ge or Al)-based anodes solves prior art problems of co-intercalation of the piperidinium cations along with the Li-ion in graphite-based electrodes at lower potentials during the charge-discharge process—as metalloid-based anodes do not co-intercalate the piperidinium cations. Nevertheless, some embodiments comprise using disclosed electrolytes 105 with ionic liquid additives 135 in lithium ion cells employing graphite anodes.

FIG. 3D is a high level schematic illustration of some of the considerations in determining an amount of ionic liquid additive 135, according to some embodiments of the invention. The considerations are shown schematically as the cross-hatched arrows. The amount of ionic liquid additive 135 in electrolyte 105, may be determined according to the specific parameters and characteristics of cells 150 (see schematic FIGS. 8A and 8B below) such as the type of the anode active material from which anode material particles 110 are made, the expansion coefficient of the anode active material, the expected and/or specified extent of expansion of anode material particles 110 during operation (see, e.g., FIG. 3C), expected level of cracking in the SEI (see, e.g., FIG. 3B) parameters of anode material particles 110 such as dimensions (diameter, volume, surface area), relative amount and number in anode 100, anode porosity, coatings of particles 110 and/or other materials in anode 100 (see e.g., FIG. 1B), as well as parameters of electrolyte 105 and its components, such as their molecular weight, density, reactivity towards the anode active material, ionic conductivity and the amount of electrolyte, and clearly according to the specific parameters and characteristics of ionic liquid additive(s) 135 such as size, molecular weight, form, electrostatic characteristics of the respective cation(s) 132 and anion(s) 131 (see, e.g., FIG. 2C), and the expected and/or specified number of layers of ionic liquid additive(s) 135 on anode material particles 110 during charging (see, e.g., FIGS. 2B and 2D). A few (non-limiting) of these considerations are illustrated in FIG. 3D schematically by the cross-hatched arrows, namely the type, expansion characteristics and dimensions of anode material particles 110, the number of layers of cations 132 and anions 131 of ionic liquid additive 135 which take part in MSEI 130 (indicated schematically as 130(1 . . . n), for non-limiting n=2 and n=4), which may further depend, among other parameters on the expansion state of anode material particles 110 and on other ingredients of electrolyte 105, and the shape, size, and electrostatic characteristics of cation(s) 132 and anion(s) 131 of ionic liquid additive(s) 135.

For example, in quantitative, non-limiting examples, assuming germanium as anode active material which may reach 270% expansion upon lithiation, and particle diameter of 100 nm, the surface area per particle upon lithiation may increase from ca. 31,000 nm² to ca. 61,000 nm². Depending on the number of required ionic liquid additive molecular layers 130(1 . . . n) and on the molecule area, the number of required ionic liquid molecules for covering the overall surface area of the anode active material particles may be calculated. For example, in a non-limiting calculation assuming three layers (n=3) at the maximal expansion of the particles and N,N-Diethyl-N-methyl-N-propylammonium (cation 132) and bis(fluorosulfonyl)imide (anion 131) as ionic liquid additive 135 (relating to cations 132 thereof for molecule size calculation—ca. 0.3 nm²), ca. 620,000 molecules are required per particle, or ca. 10⁻¹⁸ mol ionic liquid additive 135. Proceeding with estimating the overall number of particles, their mass, the molar weight of the electrolyte and the ionic liquid additive, the volume % of ionic liquid additive 135 may be calculated. For example, for 70% active material in the anode, the number of particle was estimated as ca. 5·10¹¹, requiring ca. 5·10⁻⁷ mol of ionic liquid additive 135 which is equivalent to ca. 0.05 mol/liter ionic liquid additive in electrolyte 105 (assuming electrolyte 85 comprising FEC:DMC (3:7) and 2% VC—FEC denoting fluorinated ethylene carbonates, DMC denoting dimethyl carbonate and VC denoting vinylene carbonate), or ca. 1.2% vol of ionic liquid additive 135 in electrolyte 105. Clearly, any adaptation of electrolyte 105 with respect to its ingredients, as well as any modification of the required number of layers 130 (e.g., n=1, 2, 5, 10 etc.) in expanded state yields different percentage, which may be taken into account when preparing electrolyte 105. For example, in certain embodiments, ionic liquid additive 135 concentration of 0.4% vol may be sufficient to provide one layer 130 at most expanded state of anode material particles 110 which corresponds to full lithiation. In other embodiments, lower percentage of active material in the anode may require using less ionic liquid additive 135, but not necessarily at a linear relation.

Similar calculations may be carried out for other anode active materials such as silicon (which may reach 400% expansion upon lithiation), tin (which may reach 330% expansion upon lithiation), alloys and/or mixtures thereof (with or without germanium) which may have intermediate expansion coefficients, and even less expanding anode active materials such as graphite (which typically expands by 10% upon intercalation), LTO (lithium titanate oxide) with minimal expansion (0.02%). Similar calculations may be carried out with respect to particle sizes and surface area, various types of ionic liquid 135 and various types of electrolyte 105, which are disclosed herein. The calculations presented above may be modified to determine the required concentration of ionic liquid additive 135 in electrolyte 105 using the corresponding materials.

Concluding from the examples presented above, the concentration of ionic liquid additive 135 in electrolyte 105 may be determined according to the disclosed guidelines and may vary greatly from embodiment to embodiment. While large concentrations of up to 20% may be used, some embodiments may comprise lower concentrations of 1% vol, 1-0.1% vol, 2-0.1% vol, or possibly even concentrations lower than 0.1%.

FIGS. 4A and 4B are high level schematic illustrations of an immobilized/mobilized SEI (I/MSEI) during charging and discharging, according to some embodiments of the invention. In certain embodiments, surface functionalization of the anode active material may enhance the functionality of MSEI 130, e.g., by increasing the affinity of ionic liquid 135 to the active material—electrolyte interface, and protect the interface from direct interaction with the organic solvent (of electrolyte 85). Surface functionalization may be applied by anode coatings or pre-coatings and/or by additional modifications of surface 112 of anode 100 (e.g., of anode material particles 110) and/or of the active material on anode surface 112. For example, a chemically bonded coating 145 of bonding molecules 116 such as large volume salt(s) on active material surface 112 may be used to keep some of ionic liquid 135 on surface 112 and reduce the probability of the organic solvent decomposition prior to the MSEI re-arrangement at the interface. FIGS. 4A and 4B schematically illustrate this effect by the retainment of at least some of cations 132 bonded to surface 112 even when the cell is not charged. FIGS. 4A and 4B schematically illustrate anode 100 (e.g., anode material particles 110) during charging 101C and discharging (or no charging, 101D) with ionic liquid additive 135 building MSEI 130 in charging state 101C, which may comprise an immobilized section 140A and a mobile section 140B, the former remaining in discharging state 101D bonded or associate with anode surface while the latter returning into electrolyte 105 in discharging state 101D. Coating 145 may represent a layer in which bonding molecules 116 are associated with an anode coating and/or attached to anode 100. Cations 132C and possibly anions 131C which stay bonded to bonding molecules 116 (immobilized section 140A of ionic liquid additive 135) are denoted differently from cations 132B and anions 131B which stay in electrolyte 105 (mobile section 140B of ionic liquid additive 135), to illustrate that a part (or possibly all) of electrolyte additive 135 is immobilized onto layer 145 of anode 100 during operation of the cell. Immobilized layer 140A at the interface may have a better affinity to ionic liquid 135 and less affinity toward organic solvent of electrolyte 85, and therefore keep the organic solvent away from the interface and reduce the probability for its decomposition.

In some embodiments, the bonding of ions of ionic liquid additive(s) 135 may involve bonding cations 132 or possibly anions 131 by bonding molecules 116 as the layer closest to surface 112. The bonding may be carried out during one or more first charging and discharging cycles of cell 150. In certain embodiments, the bonding of cations 132 and/or anions 131 may be carried out, at least partially, on active material 110 itself, even before the first charging cycle. The bonding of the ionic liquid to bonding layer 145 may be electrostatic and/or salt-like (ionic). In certain embodiments, the bonding may be at least partly covalent. The bonding may involve any number of ionic layers, typically a few layers, possibly providing a salt layer which isolates the organic solvent used for electrolyte 85 at least from active material 110 of anode 100.

Bonding molecules 116 may be ionic or have electron rich groups such as sodium aniline sulfonate. Bonding molecules 116 may comprise lithium cations and/or possibly magnesium cations, the latter possibly when the anode material is graphite. Non-limiting examples for bonding molecules 116 comprise lithium alkylsulfonate, poly(lithium alkylsulfonate), lithium sulfate, lithium phosphate, lithium phosphate monobasic, alkylhydroxamate salts and their acidic forms (e.g., lithium sulfonic acid, LiHSO₄, instead of lithium sulfonate, Li₂SO₄). In case of aluminum as anode material, bonding molecules 116 may comprise lithium cations and/or aluminum cations. The lithium in the following examples may thus be replaced in some embodiments by magnesium and/or aluminum. In case of graphite anodes, a wide range of activation techniques which yield oxidized graphite may be used to enhance chemical bonding of molecules 116 (e.g., using halides or alkoxides). See below an elaboration of bonding molecules 116 and their characteristics.

The chemical bonding of molecules 116 to anode 100 (e.g., to anode material particles 110) may be carried out, for example, in the anode slurry solution and/or in dry ball milling with anode material particles. The bonding mechanism may comprise, e.g., reaction(s) of the lithium sulfonates and/or salts with metal oxides, releasing the oxide and creating a direct chemical bond to metalloid surface 112, where the lithium cation remain partly charged (Li^(δ+)) in the metalloid. For example, using a large volume salt with an additional anion group as bonding molecules 116 may create a salt surface 145 on metalloid material 110, which can both protect the interface and co-operate with ionic liquid additive 135 in electrolyte 105. Layer 145 may bind a stationary portion of ionic liquid additive 135 on metalloid surface 112 while the rest of ionic liquid additive 135 is mobilized in electrolyte 105, providing a hybrid ionic liquid additive which is partly bonded and partly free in electrolyte 105. Stationary portion 140A may increase the re-ordering rate of ionic liquid additive 135 on surface 115 during charging (101C), help repel organic electrolyte 85 from the interface and hence reduce the probability for the decomposition of the organic solvent. Non-limiting examples for bonding molecules 116 include large anionic salts or their acids which may be selected to sterically repel the smaller organic carbonates solvents (of electrolyte 85) from active material surface 112. Layer 145 and stationary portion 140A of ionic liquid additive 135 on metalloid surface 112 may be highly effective during the initial charging, and enable or support the building of a stable SEI during the formation cycle(s) which protects surface 112 and anode 100 during later operation, and prevent decomposition of electrolyte on anode 100 as well as lithium metallization thereupon.

The resulting SEI may be modified toward enhanced stability and be possibly provided with self-healing mechanisms through layer 145 and stationary portion 140A of ionic liquid additive 135.

In some embodiments, bonding molecules 116 are represented by formula I:

wherein:

-   each Z is independently selected from aryl, heterocycloalkyl, crown     etheryl, cyclamyl, cyclenyl, 1,4,7-Triazacyclononanyl, hexacyclenyl,     cryptandyl, naphthalenyl, anthracenyl, phenanthrenyl, tetracenyl,     chrysenyl, triphenylenyl pyrenyl and pentacenyl; -   R¹ is [C(L¹)₂]_(q) ¹-R¹⁰¹; -   each L¹ is independently selected from H, F and R¹⁰¹; -   R², R³, R⁴, R⁵, R⁶ and R¹⁰¹ are each independently selected from     CO₂H, CO₂M¹, CO₂R, SO₃H, SO₃M¹, PO₃H₂, PO₃M¹ _(2.) PO₃M¹H, PO₄H₂,     PO₄M¹ ₂, PO₄M¹H, PO₄M², C(O)NHOH, NH₂, NHR, N(R)₂, NO₂, COOR, CHO,     CH₂OH, OH, OR, SH, SR, C(O)N(R)₂, C(O)NHR, C(O)NH₂, halide,     tosylate, mesylate, SO₂NHR, triflate, isocyanate, cyanate,     thiocyanate, isothiocyanate, R, cyano, CF₃, and Si(OR)₃; -   each R is independently selected from methyl, ethyl, isopropyl,     n-propyl, alkyl, haloalkyl, cycloalkyl, heterocycloalkyl, aryl, and     benzyl; -   each M¹ is independently Li, Na, K, Rb or Cs; -   each M² is independently Be, Mg, Ca, Sr or Ba; -   T¹ and T² are each independently absent, or selected from H, CO₂H,     CO₂M¹, CO₂R, SO₃H, SO₃M¹, PO₃H₂, PO₃M¹ _(2.) PO₃M¹H, PO₄H₂, PO₄M¹ ₂,     PO₄M¹H, PO₄M², C(O)NHOH, NH₂, NHR, N(R)₂, NO₂, COOR, CHO, CH₂OH, OH,     OR, SH, SR, C(O)N(R)₂, C(O)NHR, C(O)NH₂, halide, tosylate, mesylate,     SO₂NHR, triflate, isocyanate, cyanate, thiocyanate, isothiocyanate,     R, cyano, CF₃, and Si(OR)₃; -   m¹, m², m³, m⁴, m⁵, and m⁶ are each independently an integer between     0-6; -   n¹ is an integer between 1-10; -   q¹ is an integer between 0-10; and -   Z is connected to any of R¹-R⁶, T¹-T² or to any neighboring     repeating unit in any possible substitution position and via one or     more atoms.

In some embodiments, bonding molecules 116 are represented by formula II:

wherein:

-   R⁷ is [C(L²)₂]_(q) ²-R¹⁰²; -   each L² is independently selected from H, F and R¹⁰²; -   R⁸, R⁹, R¹⁰, R¹¹, R¹² and R¹⁰² are each independently selected from     CO₂H, CO₂M¹, CO₂R, SO₃H, SO₃M¹, PO₃H₂, PO₃M¹ _(2.) PO₃M¹H, PO₄H₂,     PO₄M¹ ₂, PO₄M¹H, PO₄M², C(O)NHOH, NH₂, NHR, N(R)₂, NO₂, COOR, CHO,     CH₂OH, OH, OR, SH, SR, C(O)N(R)₂, C(O)NHR, C(O)NH₂, halide,     tosylate, mesylate, SO₂NHR, triflate, isocyanate, cyanate,     thiocyanate, isothiocyanate, R, cyano and Si(OR)₃; -   each R is independently selected from methyl, ethyl, isopropyl,     n-propyl, alkyl, haloalkyl, cycloalkyl, heterocycloalkyl, aryl, and     benzyl; -   each M¹ is independently Li, Na, K. Rb or Cs; -   each M² is independently Be, Mg, Ca, Sr or Ba; -   m⁷, m⁸, m⁹, m¹⁰, m¹¹ and m¹² are each independently an integer     between 0-6; and -   q² is an integer between 0-10.

In some embodiments, bonding molecules 116 are represented by formula III: (L³)₃C—R¹⁰³   (III) wherein

-   R¹⁰³ is [C(L⁴)₂]_(q) ³-R¹⁰⁵; -   each L³ is independently selected from H, F and R¹⁰⁴; -   each L⁴ is independently selected from H, F and R¹⁰⁶; -   R¹⁰⁴, R¹⁰⁵, and R¹⁰⁶ are each independently selected from CO₂H,     CO₂M¹, CO₂R, SO₃H, SO₃M¹, PO₃H₂, PO₃M¹ _(2.) PO₃M¹H, PO₄H₂, PO₄M¹ ₂,     PO₄M¹H, PO₄M², C(O)NHOH, NH₂, NHR, N(R)₂, NO₂, COOR, CHO, CH₂OH, OH,     OR, SH, SR, C(O)N(R)₂, C(O)NHR, C(O)NH₂, halide, tosylate, mesylate,     SO₂NHR, triflate, isocyanate, cyanate, thiocyanate, isothiocyanate,     R, cyano, CF₃ and Si(OR)₃; -   each R is independently selected from methyl, ethyl, isopropyl,     n-propyl, alkyl, haloalkyl, cycloalkyl, heterocycloalkyl, aryl, or     benzyl; -   each M¹ is independently Li, Na, K, Rb or Cs; -   each M² is independently Be, Mg, Ca, Sr or Ba; and -   q³ is an integer between 0-10.

In some embodiments, bonding molecules 116 are represented by formula IV:

wherein:

-   X¹ and X² are each independently selected from S, O and CH₂; -   R¹³ and R¹⁴ are each independently selected from CO₂H, CO₂M¹, CO₂R,     SO₃H, SO₃M¹, PO₃H₂, PO₃M¹ _(2.) PO₃M¹H, PO₄H₂, PO₄M¹ ₂, PO₄M¹H,     PO₄M², C(O)NHOH, NH₂, NHR, N(R)₂, NO₂, COOR, CHO, CH₂OH, OH, OR, SH,     SR, C(O)N(R)₂, C(O)NHR, C(O)NH₂, halide, tosylate, mesylate, SO₂NHR,     triflate, isocyanate, cyanate, thiocyanate, isothiocyanate, R,     cyano, CF₃ and Si(OR)₃; -   each M¹ is independently Li, Na, K, Rb or Cs; -   each M² is independently Be, Mg, Ca, Sr or Ba; -   each R is independently selected from methyl, ethyl, isopropyl,     n-propyl, alkyl, haloalkyl, cycloalkyl, heterocycloalkyl, aryl, or     benzyl; and -   n², n³, n⁴ and n⁵ are each independently an integer between 0-10

In some embodiments, bonding molecules 116 are represented by formula V:

wherein:

-   X³ and X⁴ are each independently selected from S, O and CH₂; -   R¹⁵ and R¹⁶ are each independently selected from CO₂H, CO₂M¹, CO₂R,     SO₃H, SO₃M¹, PO₃H₂, PO₃M¹ _(2.) PO₃M¹H, PO₄H₂, PO₄M¹ ₂, PO₄M¹H,     PO₄M², C(O)NHOH, NH₂, NHR, N(R)₂, NO₂, COOR, CHO, CH₂OH, OH, OR, SH,     SR, C(O)N(R)₂, C(O)NHR, C(O)NH₂, halide, tosylate, mesylate, SO₂NHR,     triflate, isocyanate, cyanate, thiocyanate, isothiocyanate, R,     cyano, CF₃ and Si(OR)₃; -   each M¹ is independently Li, Na, K, Rb or Cs; -   each M² is independently Be, Mg, Ca, Sr or Ba; -   each R is independently selected from methyl, ethyl, isopropyl,     n-propyl, alkyl, haloalkyl, cycloalkyl, heterocycloalkyl, aryl, or     benzyl; and -   n⁶, and n⁷ are each independently an integer between 0-10

In some embodiments, bonding molecules 116 are represented by formula VI:

wherein:

-   each R¹⁷ is independently selected from CO₂H, CO₂M¹, CO₂R, SO₃H,     SO₃M¹, PO₃H₂, PO₃M¹ _(2.) PO₃M¹H, PO₄H₂, PO₄M¹ ₂, PO₄M¹H, PO₄M²,     C(O)NHOH, NH₂, NHR, N(R)₂, NO₂, COOR, CHO, CH₂OH, OH, OR, SH, SR,     C(O)N(R)₂, C(O)NHR, C(O)NH₂, halide, tosylate, mesylate, SO₂NHR,     triflate, isocyanate, cyanate, thiocyanate, isothiocyanate, R,     cyano, CF₃ and Si(OR)₃; -   T³ and T⁴ are each independently selected from H, CO₂H, CO₂M¹, CO₂R,     SO₃H, SO₃M¹, PO₃H₂, PO₃M¹ _(2.) PO₃M¹H, PO₄H₂, PO₄M¹ ₂, PO₄M¹H,     PO₄M², C(O)NHOH, NH₂, NHR, N(R)₂, NO₂, COOR, CHO, CH₂OH, OH, OR, SH,     SR, C(O)N(R)₂, C(O)NHR, C(O)NH₂, halide, tosylate, mesylate, SO₂NHR,     triflate, isocyanate, cyanate, thiocyanate, isothiocyanate, R,     cyano, CF₃ and Si(OR)₃; -   each M¹ is independently Li, Na, K, Rb or Cs; -   each M² is independently Be, Mg, Ca, Sr or Ba; -   each R is independently selected from methyl, ethyl, isopropyl,     n-propyl, alkyl, haloalkyl, cycloalkyl, heterocycloalkyl, aryl, or     benzyl; and -   n⁸ is an integer between 2-10000.

In some embodiments, bonding molecules 116 are represented by formula VII:

wherein:

-   R¹⁸, R¹⁹, R²⁰, R²¹ and R²² are each independently selected from     CO₂H, CO₂M¹, CO₂R, SO₃H, SO₃M¹, PO₃H₂, PO₃M¹ _(2.) PO₃M¹H,     PO₄H₂,PO₄M¹ ₂, PO₄M¹H, PO₄M², C(O)NHOH, NH₂, NHR, N(R)₂, NO₂, COOR,     CHO, CH₂OH, OH, OR, SH, SR, C(O)N(R)₂, C(O)NHR, C(O)NH₂, halide,     tosylate, mesylate, SO₂NHR, triflate, isocyanate, cyanate,     thiocyanate, isothiocyanate, R, cyano CF₃ and Si(OR)₃; -   T⁵ and T⁶ are each independently selected from H, CO₂H, CO₂M¹, CO₂R,     SO₃H, SO₃M¹, PO₃H₂, PO₃M¹ _(2.) PO₃M¹H, PO₄H₂, PO₄M¹ ₂, PO₄M¹H,     PO₄M², C(O)NHOH, NH₂, NHR, N(R)₂, NO₂, COOR, CHO, CH₂OH, OH, OR, SH,     SR, C(O)N(R)₂, C(O)NHR, C(O)NH₂, halide, tosylate, mesylate, SO₂NHR,     triflate, isocyanate, cyanate, thiocyanate, isothiocyanate, R,     cyano, CF₃ and Si(OR)₃; -   each M¹ is independently Li, Na, K, Rb or Cs; -   each M² is independently Be, Mg, Ca, Sr or Ba; -   each R is independently selected from methyl, ethyl, isopropyl,     n-propyl, alkyl, haloalkyl, cycloalkyl, heterocycloalkyl, aryl, and     benzyl; -   n⁹ is an integer between 20-10000; and -   m⁷, m⁸, m⁹, m¹⁰, m¹¹ and m¹² are each independently an integer     between 0-5.

In some embodiments, bonding molecules 116 may be polymers, possibly crosslinked with inorganic crosslinkers. Non limiting examples of polymers include polymers represented by formula VI, polyvinylalcohol (PVA), polymethylmetacrylate (PMMA), polyacrylic acid (PAA), polyethylene glycol (PEG), polyvinylsulfonic acid and polyvinylpyrrolidone (PVP), or any combination thereof. Non limiting examples of inorganic crosslinkers include boron (B) oxides, zirconium complexes and tetralkoxysilanes or any combination thereof. Non limiting examples of boron (B) oxides include boric acid (H₃BO₃), salts of tetraborate (B₄O₇ ²⁻) and boron trioxide (B₂O₃). In some embodiments, salts of tetraborate (B₄O₇ ²⁻) are selected from the anion tetraborate and a cation of alkali metal or alkaline earth metal, aluminum cation (Al³⁺) or any combination thereof. In some embodiments, the boron (B) oxide is a lithium tetraborate salt (Li₂B₄O₇) (and see also borate salts 102A). Non limiting examples of zirconium complexes include zirconium complex of tetra-2-hydroxypropyl ethylenediamine and ammonium zirconium carbonate. Non limiting examples of tetraalkoxysilane include teraettioxysilane and tetrapropoxylsilane.

In some embodiments, bonding molecules 116 may comprise salts comprising cations selected from H⁺, Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr and Ba, Al³⁺ or any combination thereof and anions selected from RCOO⁻, RSO₃ ⁻, RPO₃ ²⁻, RPO₄ ²⁻ or any combination thereof. In some embodiments, the salt is lithium sulfate (Li₂SO₄). In some embodiments, the salt is lithium phosphate monobasic (H₂LiPO₄). In some embodiments, the salt is lithium phosphate (Li₃PO₄). In some embodiments, the salt is phosphoric acid (H₃PO₄).

In some embodiments, bonding molecules 116 are represented at least by one of formulas I-VII.

In some embodiments, the invention is directed to a lithium ion cell comprising a modified graphite anode, represented by the formula Gr-Bz, wherein Gr is graphite anode and Bz is a benzyl moiety. In some embodiments, a benzyl moiety with a good leaving group is reacted with graphite anode and also with a non-nucleophilic base to form a modified graphite anode, wherein the graphite is attached covalently to the CH₂ moiety of the benzylic compound. Non-limiting examples of non-nucleophilic bases include 1,8-Diazabicyclo(5.4.0)undec-7-ene (DBU), N,N-Diisopropylethylamine (DIPEA) and 2,6-Di-tert-butylpyridine. In some embodiments, the non-nucleophilic base is 1,8-Diazabicyclo(5.4.0)undec-7-ene (DBU). In some embodiments the non-nucleophilic base is N,N-Diisopropylethylamine (DIPEA). In some embodiments the non-nucleophilic base is 2,6-Di-tert-butylpyridine. In some embodiments the non-nucleophilic base is any combination of the above referenced non nucleophilic bases. Non limiting examples of good leaving groups are selected from halides (e.g., Cl, Br, I), mesylate, triflate and tosylate.

In some embodiments, the invention directs to a lithium ion cell comprising a modified graphite anode, represented by the formula Gr-SR, wherein Gr is graphite anode, SR is a thiolether moiety, wherein R is selected from alkyl, haloalkyl, cycloalkyl, heterocycloalkyl, aryl, and benzyl. In some embodiments, a thiol, RSH, is reacted with graphite anode and a radical initiator, to form a modified graphite anode, wherein the graphite is attached covalently to the S atom of the thiolether compound. Non-limiting examples of a radical initiator include azo compounds such as azobisisobutyronitrile (AIBN) and 1,1′-Azobis(cyclohexanecarbonitrile) (ABCN), organic peroxides such as benzoyl peroxide and ditertbutylperoxide and inorganic peroxides, e.g. peroxydisulfate. In some embodiments, the radical initiator is azobisisobutyronitrile (AIBN). In some embodiments, the radical initiator is 1,1′-Azobis(cyclohexanecarbonitrile) (ABCN). In some embodiments, the radical initiator is benzoyl peroxide. In some embodiments, the radical initiator is ditertbutylperoxide. In some embodiments, the radical initiator is peroxydisulfate. In some embodiments, the radical initiator is any combination of the above referenced radical initiators.

In some embodiments, the invention directs to a lithium ion cell comprising a modified Si anode. In some embodiments, the Si anode is connected covalently to bonding molecule 116, represented by formula I-VII. In some embodiments, a Si anode rich in silanol bonds, Si—OH, is reacted with the bonding molecule to afford the modified Si anode. In some embodiments, a Si anode rich in silanol bonds, Si—OH, is reacted with Si(OR)₃ moiety in the bonding molecule to afford the modified Si anode. In some embodiments, bonding molecule 116, represented by formula I-VII, is connected to the Si anode via silanol linkage, Si—O—Si.

In some embodiments, Z is aryl, heterocycloalkyl, crown etheryl, cyclamyl, cyclenyl, cryptandyl, naphthalenyl, anthracenyl, phenanthrenyl, tetracenyl, chrysenyl, triphenylenyl pyrenyl or pentacenyl. In some embodiments, Z is aryl. In some embodiments, Z is heterocycloalkyl. In some embodiments, Z is crown etheryl. In some embodiments, Z is cyclamyl. In some embodiments, Z is cyclenyl. In some embodiments, Z is cryptandyl. In some embodiments, Z is naphthalenyl. In some embodiments, Z is anthracenyl. In some embodiments, Z is anthracenyl. In some embodiments, Z is phenanthrenyl. In some embodiments, Z is tetracenyl. In some embodiments, Z is chrysenyl. In some embodiments, Z is triphenylenyl. In some embodiments, Z is pyrenyl. In some embodiments, Z is pentacenyl.

In some embodiments, L¹ is H, F or R¹⁰¹. In some embodiments, L¹ is H. In some embodiments, L¹ is F. In some embodiments, L¹ is R¹⁰¹.

In some embodiments, L² is H, F or R¹⁰². In some embodiments, L² is H. In some embodiments, L² is F. In some embodiments, L² is R¹⁰².

In some embodiments, L³ is H, F or R¹⁰⁴. In some embodiments, L³ is H. In some embodiments, L³ is F. In some embodiments, L³ is R¹⁰⁴.

In some embodiments, L⁴ is H, F or R¹⁰⁶. In some embodiments, L⁴ is H. In some embodiments, L⁴ is F. In some embodiments, L⁴ is R¹⁰⁶.

In some embodiments, R² is CO₂H, CO₂M¹, CO₂R, SO₃H, SO₃M¹, PO₃H₂, PO₃M¹ _(2.) PO₃M¹H, PO₄H₂, PO₄M¹ ₂, PO₄M¹H, PO₄M², C(O)NHOH, NH₂, NHR, N(R)₂, NO₂, COOR, CHO, CH₂OH, OH, OR, SH, SR, C(O)N(R)₂, C(O)NHR, C(O)NH₂, halide, tosylate, mesylate, SO₂NHR, triflate, isocyanate, cyanate, thiocyanate, isothiocyanate, R, cyano CF₃ or Si(OR)₃. In some embodiments, R² is CO₂H. In some embodiments, R² is CO₂M¹. In some embodiments, R² is CO₂R. In some embodiments, R² is SO₃H. In some embodiments, R² is SO₃M¹. In some embodiments, R² is PO₃H₂. In some embodiments, R² is PO₃M¹ ₂. In some embodiments, R² is PO₃M¹H. In some embodiments, R² is PO₄H₂. In some embodiments, R² is PO₄M¹ ₂. In some embodiments, R² is PO₄M¹H. In some embodiments, R² is PO₄M². In some embodiments, R² is C(O)NHOH. In some embodiments, R² is NH₂. In some embodiments, R² is NHR. In some embodiments, R² is N(R)₂. In some embodiments, R² is NO₂. In some embodiments, R² is COOR. In some embodiments, R² is CHO. In some embodiments, R² is CH₂OH. In some embodiments, R² is OH. In some embodiments, R² is OR. In some embodiments, R³ is SH. In some embodiments, R² is SR. In some embodiments, R² is C(O)N(R)₂. In some embodiments, R² is C(O)NHR. In some embodiments, R² is C(O)NH₂. In some embodiments, R² is halide. In some embodiments, R² is tosylate. In some embodiments, R² is mesylate. In some embodiments, R² is SO₂NHR. In some embodiments, R² is triflate. In some embodiments, R² is isocyanate. In some embodiments, R² is cyanate. In some embodiments, R² is thiocyanate. In some embodiments, R² is isothiocyanate. In some embodiments, R² is R. In some embodiments, R² is cyano. In some embodiments, R² is CF₃. In some embodiments, R² is Si(OR)₃.

In some embodiments, R³ is CO₂H, CO₂M¹, CO₂R, SO₃H, SO₃M¹, PO₃H₂, PO₃M¹ _(2.) PO₃M¹H, PO₄H₂, PO₄M¹ ₂, PO₄M¹H, PO₄M², C(O)NHOH, NH₂, NHR, N(R)₂, NO₂, COOR, CHO, CH₂OH, OH, OR, SH, SR, C(O)N(R)₂, C(O)NHR, C(O)NH₂, halide, tosylate, mesylate, SO₂NHR, triflate, isocyanate, cyanate, thiocyanate, isothiocyanate, R, cyano CF₃ or Si(OR)₃. In some embodiments, R³ is CO₂H. In some embodiments, R³ is CO₂M¹. In some embodiments, R³ is CO₂R. In some embodiments, R³ is SO₃H. In some embodiments, R³ is SO₃M¹. In some embodiments, R³ is PO₃H₂. In some embodiments, R³ is PO₃M¹ ₂. In some embodiments, R³ is PO₃M¹H. In some embodiments, R³ is PO₄H₂. In some embodiments, R³ is PO₄M¹ ₂. In some embodiments, R³ is PO₄M¹H. In some embodiments, R³ is PO₄M². In some embodiments, R³ is C(O)NHOH. In some embodiments, R³ is NH₂. In some embodiments, R³ is NHR. In some embodiments, R³ is N(R)₂. In some embodiments, R³ is NO₂. In some embodiments, R³ is COOR. In some embodiments, R³ is CHO. In some embodiments, R³ is CH₂OH. In some embodiments, R³ is OH. In some embodiments, R³ is OR. In some embodiments, R³ is SH. In some embodiments, R³ is SR. In some embodiments, R³ is C(O)N(R)₂. In some embodiments, R³ is C(O)NHR. In some embodiments, R³ is C(O)NH₂. In some embodiments, R³ is halide. In some embodiments, R³ is tosylate. In some embodiments, R³ is mesylate. In some embodiments, R³ is SO₂NHR. In some embodiments, R³ is triflate. In some embodiments, R³ is isocyanate. In some embodiments, R³ is cyanate. In some embodiments, R³ is thiocyanate. In some embodiments, R³ is isothiocyanate. In some embodiments, R³ is R. In some embodiments, R³ is cyano. In some embodiments, R³ is CF₃. In some embodiments, R³ is Si(OR)₃.

In some embodiments, R⁴ is CO₂H, CO₂M¹, CO₂R, SO₃H, SO₃M¹, PO₃H₂, PO₃M¹ _(2.) PO₃M¹H, PO₄H₂, PO₄M¹ ₂, PO₄M¹H, PO₄M², C(O)NHOH, NH₂, NHR, N(R)₂, NO₂, COOR, CHO, CH₂OH, OH, OR, SH, SR, C(O)N(R)₂, C(O)NHR, C(O)NH₂, halide, tosylate, mesylate, SO₂NHR, triflate, isocyanate, cyanate, thiocyanate, isothiocyanate, R, cyano CF₃ or Si(OR)₃. In some embodiments, R⁴ is CO₂H. In some embodiments, R⁴ is CO₂M¹. In some embodiments, R⁴ is CO₂R. In some embodiments, R⁴ is SO₃H. In some embodiments, R⁴ is SO₃M¹. In some embodiments, R⁴ is PO₃H₂. In some embodiments, R⁴ is PO₃M¹ ₂. In some embodiments, R⁴ is PO₃M¹H. In some embodiments, R⁴ is PO₄H₂. In some embodiments, R⁴ is PO₄M¹ ₂. In some embodiments, R⁴ is PO₄M¹H. In some embodiments, R⁴ is PO₄M². In some embodiments, R⁴ is C(O)NHOH. In some embodiments, R⁴ is NH₂. In some embodiments, R⁴ is NHR. In some embodiments, R⁴ is N(R)₂. In some embodiments, R⁴ is NO₂. In some embodiments, R⁴ is COOR. In some embodiments, R⁴ is CHO. In some embodiments, R⁴ is CH₂OH. In some embodiments, R⁴ is OH. In some embodiments, R⁴ is OR. In some embodiments, R⁴ is SH. In some embodiments, R⁴ is SR. In some embodiments, R⁴ is C(O)N(R)₂. In some embodiments, R⁴ is C(O)NHR. In some embodiments, R⁴ is C(O)NH₂. In some embodiments, R⁴ is halide. In some embodiments, R⁴ is tosylate. In some embodiments, R⁴ is mesylate. In some embodiments, R⁴ is SO₂NHR. In some embodiments, R⁴ is triflate. In some embodiments, R⁴ is isocyanate. In some embodiments, R⁴ is cyanate. In some embodiments, R⁴ is thiocyanate. In some embodiments, R⁴ is isothiocyanate. In some embodiments, R⁴ is R. In some embodiments, R⁴ is cyano. In some embodiments, R⁴ is CF₃. In some embodiments, R⁴ is Si(OR)₃.

In some embodiments, R⁵ is CO₂H, CO₂M¹, CO₂R, SO₃H, SO₃M¹, PO₃H₂, PO₃M¹ _(2.) PO₃M¹H, PO₄H₂, PO₄M¹ ₂, PO₄M¹H, PO₄M², C(O)NHOH, NH₂, NHR, N(R)₂, NO₂, COOR, CHO, CH₂OH, OH, OR, SH, SR, C(O)N(R)₂, C(O)NHR, C(O)NH₂, halide, tosylate, mesylate, SO₂NHR, triflate, isocyanate, cyanate, thiocyanate, isothiocyanate, R, cyano CF₃ or Si(OR)₃. In some embodiments, R⁵ is CO₂H. In some embodiments, R⁵ is CO₂M¹. In some embodiments, R⁵ is CO₂R. In some embodiments, R⁵ is SO₃H. In some embodiments, R⁵ is SO₃M¹. In some embodiments, R⁵ is PO₃H₂. In some embodiments, R⁵ is PO₃M¹ ₂. In some embodiments, R⁵ is PO₃M¹H. In some embodiments, R⁵ is PO₄H₂. In some embodiments, R⁵ is PO₄M¹ ₂. In some embodiments, R⁵ is PO₄M¹H. In some embodiments, R⁵ is PO₄M². In some embodiments, R⁵ is C(O)NHOH. In some embodiments, R⁵ is NH₂. In some embodiments, R⁵ is NHR. In some embodiments, R⁵ is N(R)₂. In some embodiments, R⁵ is NO₂. In some embodiments, R⁵ is COOR. In some embodiments, R⁵ is CHO. In some embodiments, R⁵ is CH₂OH. In some embodiments, R⁵ is OH. In some embodiments, R⁵ is OR. In some embodiments, R⁵ is SH. In some embodiments, R⁵ is SR. In some embodiments, R⁵ is C(O)N(R)₂. In some embodiments, R⁵ is C(O)NHR. In some embodiments, R⁵ is C(O)NH₂. In some embodiments, R⁵ is halide. In some embodiments, R⁵ is tosylate. In some embodiments, R⁵ is mesylate. In some embodiments, R⁵ is SO₂NHR. In some embodiments, R⁵ is triflate. In some embodiments, R⁵ is isocyanate. In some embodiments, R⁵ is cyanate. In some embodiments, R⁵ is thiocyanate. In some embodiments, R⁵ is isothiocyanate. In some embodiments, R⁵ is R. In some embodiments, R⁵ is cyano. In some embodiments, R⁵ is CF₃. In some embodiments, R⁵ is Si(OR)₃.

In some embodiments, R⁶ is CO₂H, CO₂M¹, CO₂R, SO₃H, SO₃M¹, PO₃H₂, PO₃M¹ _(2.) PO₃M¹H, PO₄H₂, PO₄M¹ ₂, PO₄M¹H, PO₄M², C(O)NHOH, NH₂, NHR, N(R)₂, NO₂, COOR, CHO, CH₂OH, OH, OR, SH, SR, C(O)N(R)₂, C(O)NHR, C(O)NH₂, halide, tosylate, mesylate, SO₂NHR, triflate, isocyanate, cyanate, thiocyanate, isothiocyanate, R, cyano CF₃ or Si(OR)₃. In some embodiments, R⁶ is CO₂H. In some embodiments, R⁶ is CO₂M¹. In some embodiments, R⁶ is CO₂R. In some embodiments, R⁶ is SO₃H. In some embodiments, R⁶ is SO₃M¹. In some embodiments, R⁶ is PO₃H₂. In some embodiments, R⁶ is PO₃M¹ ₂. In some embodiments, R⁶ is PO₃M¹H. In some embodiments, R⁶ is PO₄H₂. In some embodiments, R⁶ is PO₄M¹ ₂. In some embodiments, R⁶ is PO₄M¹H. In some embodiments, R⁶ is PO₄M². In some embodiments, R⁶ is C(O)NHOH. In some embodiments, R⁶ is NH₂. In some embodiments, R⁶ is NHR. In some embodiments, R⁶ is N(R)₂. In some embodiments, R⁶ is NO₂. In some embodiments, R⁶ is COOR. In some embodiments, R⁶ is CHO. In some embodiments, R⁶ is CH₂OH. In some embodiments, R⁶ is OH. In some embodiments, R⁶ is OR. In some embodiments, R⁶ is SH. In some embodiments, R⁶ is SR. In some embodiments, R⁵ is C(O)N(R)₂. In some embodiments, R⁵ is C(O)NHR. In some embodiments, R⁵ is C(O)NH₂. In some embodiments, R⁶ is halide. In some embodiments, R⁶ is tosylate. In some embodiments, R⁶ is mesylate. In some embodiments, R⁶ is SO₂NHR. In some embodiments, R⁶ is triflate. In some embodiments, R⁶ is isocyanate. In some embodiments, R⁶ is cyanate. In some embodiments, R⁶ is thiocyanate. In some embodiments, R⁶ is isothiocyanate. In some embodiments, R⁶ is R. In some embodiments, R⁶ is cyano. In some embodiments, R⁶ is CF₃. In some embodiments, R⁶ is Si(OR)₃.

In some embodiments, R⁸ is CO₂H, CO₂M¹, CO₂R, SO₃H, SO₃M¹, PO₃H₂, PO₃M¹ _(2.) PO₃M¹H, PO₄H₂, PO₄M¹ ₂, PO₄M¹H, PO₄M², C(O)NHOH, NH₂, NHR, N(R)₂, NO₂, COOR, CHO, CH₂OH, OH, OR, SH, SR, C(O)N(R)₂, C(O)NHR, C(O)NH₂, halide, tosylate, mesylate, SO₂NHR, triflate, isocyanate, cyanate, thiocyanate, isothiocyanate, R, cyano CF₃ or Si(OR)₃. In some embodiments, R⁸ is CO₂H. In some embodiments, R⁸ is CO₂M¹. In some embodiments, R⁸ is CO₂R. In some embodiments, R⁸ is SO₃H. In some embodiments, R⁸ is SO₃M¹. In some embodiments, R⁸ is PO₃H₂. In some embodiments, R⁸ is PO₃M¹ ₂. In some embodiments, R⁵ is PO₃M¹H. In some embodiments, R⁸ is PO₄H₂. In some embodiments, R⁸ is PO₄M¹ ₂. In some embodiments, R⁸ is PO₄M¹H. In some embodiments, R⁸ is PO₄M². In some embodiments, R⁸ is C(O)NHOH. In some embodiments, R⁸ is NH₂. In some embodiments, R⁸ is NHR. In some embodiments, R⁸ is N(R)₂. In some embodiments, R⁸ is NO₂. In some embodiments, R⁸ is COOR. In some embodiments, R⁸ is CHO. In some embodiments, R⁸ is CH₂OH. In some embodiments, R⁸ is OH. In some embodiments, R⁸ is OR. In some embodiments, R⁸ is SH. In some embodiments, R⁸ is SR. In some embodiments, R⁸ is C(O)N(R)₂. In some embodiments, R⁸ is C(O)NHR. In some embodiments, R⁸ is C(O)NH₂. In some embodiments, R⁸ is halide. In some embodiments, R⁸ is tosylate. In some embodiments, R⁸ is mesylate. In some embodiments, R⁸ is SO₂NHR. In some embodiments, R⁸ is triflate. In some embodiments, R⁸ is isocyanate. In some embodiments, R⁸ is cyanate. In some embodiments, R⁸ is thiocyanate. In some embodiments, R⁸ is isothiocyanate. In some embodiments, R⁸ is R. In some embodiments, R⁸ is cyano. In some embodiments, R⁸ is CF₃. In some embodiments, R⁸ is Si(OR)₃.

In some embodiments, R⁹ is CO₂H, CO₂M¹, CO₂R, SO₃H, SO₃M¹, PO₃H₂, PO₃M¹ _(2.) PO₃M¹H, PO₄H₂, PO₄M¹ ₂, PO₄M¹H, PO₄M², C(O)NHOH, NH₂, NHR, N(R)₂, NO₂, COOR, CHO, CH₂OH, OH, OR, SH, SR, C(O)N(R)₂, C(O)NHR, C(O)NH₂, halide, tosylate, mesylate, SO₂NHR, triflate, isocyanate, cyanate, thiocyanate, isothiocyanate, R, cyano, CF₃ or Si(OR)₃. In some embodiments, R⁹ is CO₂H. In some embodiments, R⁹ is CO₂M¹. In some embodiments, R⁹ is CO₂R. In some embodiments, R⁹ is SO₃H. In some embodiments, R⁹ is SO₃M¹. In some embodiments, R⁹ is PO₃H₂. In some embodiments, R⁹ is PO₃M¹ ₂. In some embodiments, R⁹ is PO₃M¹H. In some embodiments, R⁹ is PO₄H₂. In some embodiments, R⁹ is PO₄M¹ ₂. In some embodiments, R⁹ is PO₄M¹H. In some embodiments, R⁹ is PO₄M². In some embodiments, R⁹ is C(O)NHOH. In some embodiments, R⁹ is NH₂. In some embodiments, R⁹ is NHR. In some embodiments, R⁹ is N(R)₂. In some embodiments, R⁹ is NO₂. In some embodiments, R⁹ is COOR. In some embodiments, R⁹ is CHO. In some embodiments, R⁹ is CH₂OH. In some embodiments, R⁹ is OH. In some embodiments, R⁹ is OR. In some embodiments, R⁵ is SH. In some embodiments, R⁹ is SR. In some embodiments, R⁹ is C(O)N(R)₂. In some embodiments, R⁹ is C(O)NHR. In some embodiments, R⁹ is C(O)NH₂. In some embodiments, R⁹ is halide. In some embodiments, R⁹ is tosylate. In some embodiments, R⁹ is mesylate. In some embodiments, R⁹ is SO₂NHR. In some embodiments, R⁹ is triflate. In some embodiments, R⁹ is isocyanate. In some embodiments, R⁹ is cyanate. In some embodiments, R⁹ is thiocyanate. In some embodiments, R⁹ is isothiocyanate. In some embodiments, R⁹ is R. In some embodiments, R⁹ is cyano. In some embodiments, R⁹ is CF₃. In some embodiments, R⁹ is Si(OR)₃.

In some embodiments, R¹⁰ is CO₂H, CO₂M¹, CO₂R, SO₃H, SO₃M¹, PO₃H₂, PO₃M¹ _(2.) PO₃M¹H, PO₄H₂, PO₄M¹ ₂, PO₄M¹H, PO₄M², C(O)NHOH, NH₂, NHR, N(R)₂, NO₂, COOR, CHO, CH₂OH, OH, OR, SH, SR, C(O)N(R)₂, C(O)NHR, C(O)NH₂, halide, tosylate, mesylate, SO₂NHR, triflate, isocyanate, cyanate, thiocyanate, isothiocyanate, R, cyano CF₃ or Si(OR)₃. In some embodiments, R¹⁰ is CO₂H. In some embodiments, R¹⁰ is CO₂M¹. In some embodiments, R¹⁰ is CO₂R. In some embodiments, R¹⁰ is SO₃H. In some embodiments, R¹⁰ is SO₃M¹. In some embodiments, R¹⁰ is PO₃H₂. In some embodiments, R¹⁰ is PO₃M¹ ₂. In some embodiments, R¹⁰ is PO₃M¹H. In some embodiments, R¹⁰ is PO₄H₂. In some embodiments, R¹⁰ is PO₄M¹ ₂. In some embodiments, R¹⁰ is PO₄M¹H. In some embodiments, R¹⁰ is PO₄M². In some embodiments, R¹⁰ is C(O)NHOH. In some embodiments, R¹⁰ is NH₂. In some embodiments, R¹⁰ is NHR. In some embodiments, R¹⁰ is N(R)₂. In some embodiments, R¹⁰ is NO₂. In some embodiments, R¹⁰ is COOR. In some embodiments, R¹⁰ is CHO. In some embodiments, R¹⁰ is CH₂OH. In some embodiments, R¹⁰ is OH. In some embodiments, R¹⁰ is OR. In some embodiments, R¹⁰ is SH. In some embodiments, R¹⁰ is SR. In some embodiments, R¹⁰ is C(O)N(R)₂. In some embodiments, R¹⁰ is C(O)NHR. In some embodiments, R¹⁰ is C(O)NH₂. In some embodiments, R¹⁰ is halide. In some embodiments, R¹⁰ is tosylate. In some embodiments, R¹⁰ is mesylate. In some embodiments, R¹⁰ is SO₂NHR. In some embodiments, R¹⁰ is triflate. In some embodiments, R¹⁰ is isocyanate. In some embodiments, R¹⁰ is cyanate. In some embodiments, R¹⁰ is thiocyanate. In some embodiments, R¹⁰ is isothiocyanate. In some embodiments, R¹⁰ is R. In some embodiments, R¹⁰ is cyano. In some embodiments, R¹⁰ is CF₃. In some embodiments, R¹⁰ is Si(OR)₃.

In some embodiments, R¹¹ is CO₂H, CO₂M¹, CO₂R, SO₃H, SO₃M¹, PO₃H₂, PO₃M¹ _(2.) PO₃M¹H, PO₄H₂, PO₄M¹ ₂, PO₄M¹H, PO₄M², C(O)NHOH, NH₂, NHR, N(R)₂, NO₂, COOR, CHO, CH₂OH, OH, OR, SH, SR, C(O)N(R)₂, C(O)NHR, C(O)NH₂, halide, tosylate, mesylate, SO₂NHR, triflate, isocyanate, cyanate, thiocyanate, isothiocyanate, R, cyano CF₃ or Si(OR)₃. In some embodiments, R¹¹ is CO₂H. In some embodiments, R¹¹ is CO₂M¹. In some embodiments, R¹¹ is CO₂R. In some embodiments, R¹¹ is SO₃H. In some embodiments, R¹¹ is SO₃M¹. In some embodiments, R¹¹ is PO₃H₂. In some embodiments, R¹¹ is PO₃M¹ ₂. In some embodiments, R¹¹ is PO₃M¹H. In some embodiments, R¹¹ is PO₄H₂. In some embodiments, R¹¹ is PO₄M¹ ₂. In some embodiments, R¹¹ is PO₄M¹H. In some embodiments, R¹¹ is PO₄M². In some embodiments, R¹¹ is C(O)NHOH. In some embodiments, R¹¹ is NH₂. In some embodiments, R¹¹ is NHR. In some embodiments, R¹¹ is N(R)₂. In some embodiments, R¹¹ is NO₂. In some embodiments, R¹¹ is COOR. In some embodiments, R¹¹ is CHO. In some embodiments, R¹¹ is CH₂OH. In some embodiments, R¹¹ is OH. In some embodiments, R¹¹ is OR. In some embodiments, R¹¹ is SH. In some embodiments, R¹¹ is SR. In some embodiments, R¹¹ is C(O)N(R)₂. In some embodiments, R¹¹ is C(O)NHR. In some embodiments, R¹¹ is C(O)NH₂. In some embodiments, R¹¹ is halide. In some embodiments, R¹¹ is tosylate. In some embodiments, R¹¹ is mesylate. In some embodiments, R¹¹ is SO₂NHR. In some embodiments, R¹¹ is triflate. In some embodiments, R¹¹ is isocyanate. In some embodiments, R¹¹ is cyanate. In some embodiments, R¹¹ is thiocyanate. In some embodiments, R¹¹ is isothiocyanate. In some embodiments, R¹¹ is R. In some embodiments, R¹¹ is cyano. In some embodiments, R¹¹ is CF₃. In some embodiments, R¹¹ is Si(OR)₃.

In some embodiments, R¹² is CO₂H, CO₂M¹, CO₂R, SO₃H, SO₃M¹, PO₃H₂, PO₃M¹ _(2.) PO₃M¹H, PO₄H₂, PO₄M¹ ₂, PO₄M¹H, PO₄M², C(O)NHOH, NH₂, NHR, N(R)₂, NO₂, COOR, CHO, CH₂OH, OH, OR, SH, SR, C(O)N(R)₂, C(O)NHR, C(O)NH₂, halide, tosylate, mesylate, SO₂NHR, triflate, isocyanate, cyanate, thiocyanate, isothiocyanate, R, cyano CF₃ or Si(OR)₃. In some embodiments, R¹² is CO₂H. In some embodiments, R¹² is CO₂M¹. In some embodiments, R¹² is CO₂R. In some embodiments, R¹² is SO₃H. In some embodiments, R¹² is SO₃M¹. In some embodiments, R¹² is PO₃H₂. In some embodiments, R¹² is PO₃M¹ ₂. In some embodiments, R¹² is PO₃M¹H. In some embodiments, R¹² is PO₄H₂. In some embodiments, R¹² is PO₄M¹ ₂. In some embodiments, R¹² is PO₄M¹H. In some embodiments, R¹² is PO₄M². In some embodiments, R¹² is C(O)NHOH. In some embodiments, R¹² is NH₂. In some embodiments, R¹² is NHR. In some embodiments, R¹² is N(R)₂. In some embodiments, R¹² is NO₂. In some embodiments, R¹² is COOR. In some embodiments, R¹² is CHO. In some embodiments, R¹² is CH₂OH. In some embodiments, R¹² is OH. In some embodiments, R¹² is OR. In some embodiments, R¹² is SH. In some embodiments, R¹² is SR. In some embodiments, R¹² is C(O)N(R)₂. In some embodiments, R¹² is C(O)NHR. In some embodiments, R¹² is C(O)NH₂. In some embodiments, R¹² is halide. In some embodiments, R¹² is tosylate. In some embodiments, R¹² is mesylate. In some embodiments, R¹² is SO₂NHR. In some embodiments, R¹² is triflate. In some embodiments, R¹² is isocyanate. In some embodiments, R¹² is cyanate. In some embodiments, R¹² is thiocyanate. In some embodiments, R¹² is isothiocyanate. In some embodiments, R¹² is R. In some embodiments, R¹² is cyano. In some embodiments, R¹² is CF₃. In some embodiments, R⁵ is Si(OR)₃.

In some embodiments, R¹³ is CO₂H, CO₂M¹, CO₂R, SO₃H, SO₃M¹, PO₃H₂, PO₃M¹ _(2.) PO₃M¹H, PO₄H₂, PO₄M¹ ₂, PO₄M¹H, PO₄M², C(O)NHOH, NH₂, NHR, N(R)₂, NO₂, COOR, CHO, CH₂OH, OH, OR, SH, SR, C(O)N(R)₂, C(O)NHR, C(O)NH₂, halide, tosylate, mesylate, SO₂NHR, triflate, isocyanate, cyanate, thiocyanate, isothiocyanate, R, cyano CF₃ or Si(OR)₃. In some embodiments, R¹³ is CO₂H. In some embodiments, R¹³ is CO₂M¹. In some embodiments, R¹³ is CO₂R. In some embodiments, R¹³ is SO₃H. In some embodiments, R¹³ is SO₃M¹. In some embodiments, R¹³ is PO₃H₂. In some embodiments, R¹³ is PO₃M¹ ₂. In some embodiments, R¹³ is PO₃M¹H. In some embodiments, R¹³ is PO₄H₂. In some embodiments, R¹³ is PO₄M¹ ₂. In some embodiments, R¹³ is PO₄M¹H. In some embodiments, R¹³ is PO₄M². In some embodiments, R¹³ is C(O)NHOH. In some embodiments, R¹³ is NH₂. In some embodiments, R¹³ is NHR. In some embodiments, R¹³ is N(R)₂. In some embodiments, R¹³ is NO₂. In some embodiments, R¹³ is COOR. In some embodiments, R¹³ is CHO. In some embodiments, R¹³ is CH₂OH. In some embodiments, R¹³ is OH. In some embodiments, R¹³ is OR. In some embodiments, R¹³ is SH. In some embodiments, R⁵ is SR. In some embodiments, R¹³ is C(O)N(R)₂. In some embodiments, R¹³ is C(O)NHR. In some embodiments, R¹³ is C(O)NH₂. In some embodiments, R¹³ is halide. In some embodiments, R¹³ is tosylate. In some embodiments, R¹³ is mesylate. In some embodiments, R¹³ is SO₂NHR. In some embodiments, R¹³ is triflate. In some embodiments, R¹³ is isocyanate. In some embodiments, R¹³ is cyanate. In some embodiments, R¹³ is thiocyanate. In some embodiments, R¹³ is isothiocyanate. In some embodiments, R¹³ is R. In some embodiments, R¹³ is cyano. In some embodiments, R¹³ is CF₃. In some embodiments, R¹³ is Si(OR)₃.

In some embodiments, R¹⁴ is CO₂H, CO₂M¹, CO₂R, SO₃H, SO₃M¹, PO₃H₂, PO₃M¹ _(2.) PO₃M¹H, PO₄H₂, PO₄M¹ ₂, PO₄M¹H, PO₄M², C(O)NHOH, NH₂, NHR, N(R)₂, NO₂, COOR, CHO, CH₂OH, OH, OR, SH, SR, C(O)N(R)₂, C(O)NHR, C(O)NH₂, halide, tosylate, mesylate, SO₂NHR, triflate, isocyanate, cyanate, thiocyanate, isothiocyanate, R, cyano CF₃ or Si(OR)₃. In some embodiments, R¹⁴ is CO₂H. In some embodiments, R¹⁴ is CO₂M¹. In some embodiments, R¹⁴ is CO₂R. In some embodiments, R¹⁴ is SO₃H. In some embodiments, R¹⁴ is SO₃M¹. In some embodiments, R¹⁴ is PO₃H₂. In some embodiments, R¹⁴ is PO₃M¹ ₂. In some embodiments, R¹⁴ is PO₃M¹H. In some embodiments, R¹⁴ is PO₄H₂. In some embodiments, R¹⁴ is PO₄M¹ ₂. In some embodiments, R¹⁴ is PO₄M¹H. In some embodiments, R¹⁴ is PO₄M². In some embodiments, R¹⁴ is C(O)NHOH. In some embodiments, R¹⁴ is NH₂. In some embodiments, R¹⁴ is NHR. In some embodiments, R¹⁴ is N(R)₂. In some embodiments, R¹⁴ is NO₂. In some embodiments, R¹⁴ is COOR. In some embodiments, R¹⁴ is CHO. In some embodiments, R¹⁴ is CH₂OH. In some embodiments, R¹⁴ is OH. In some embodiments, R¹⁴ is OR. In some embodiments, R¹⁴ is SH. In some embodiments, R¹⁴ is SR. In some embodiments, R¹⁴ is C(O)N(R)₂. In some embodiments, R¹⁴ is C(O)NHR. In some embodiments, R¹⁴ is C(O)NH₂. In some embodiments, R¹⁴ is halide. In some embodiments, R¹⁴ is tosylate. In some embodiments, R¹⁴ is mesylate. In some embodiments, R¹⁴ is SO₂NHR. In some embodiments, R¹⁴ is triflate. In some embodiments, R¹⁴ is isocyanate. In some embodiments, R¹⁴ is cyanate. In some embodiments, R¹⁴ is thiocyanate. In some embodiments, R¹⁴ is isothiocyanate. In some embodiments, R¹⁴ is R. In some embodiments, R¹⁴ is cyano. In some embodiments, R¹⁴ is CF₃. In some embodiments, R¹⁴ is Si(OR)₃.

In some embodiments, R¹⁵ is CO₂H, CO₂M¹, CO₂R, SO₃H, SO₃M¹, PO₃H₂, PO₃M¹ _(2.) PO₃M¹H, PO₄H₂, PO₄M¹ ₂, PO₄M¹H, PO₄M², C(O)NHOH, NH₂, NHR, N(R)₂, NO₂, COOR, CHO, CH₂OH, OH, OR, SH, SR, C(O)N(R)₂, C(O)NHR, C(O)NH₂, halide, tosylate, mesylate, SO₂NHR, triflate, isocyanate, cyanate, thiocyanate, isothiocyanate, R, cyano CF₃ or Si(OR)₃. In some embodiments, R¹⁵ is CO₂H. In some embodiments, R¹⁵ is CO₂M¹. In some embodiments, R¹⁵ is CO₂R. In some embodiments, R¹⁵ is SO₃H. In some embodiments, R¹⁵ is SO₃M¹. In some embodiments, R¹⁵ is PO₃H₂. In some embodiments, R¹⁵ is PO₃M¹ ₂. In some embodiments, R¹⁵ is PO₃M¹H. In some embodiments, R¹⁵ is PO₄H₂. In some embodiments, R¹⁵ is PO₄M¹ ₂. In some embodiments, R¹⁵ is PO₄M¹H. In some embodiments, R¹⁵ is PO₄M². In some embodiments, R¹⁵ is C(O)NHOH. In some embodiments, R¹⁵ is NH₂. In some embodiments, R¹⁵ is NHR. In some embodiments, R¹⁵ is N(R)₂. In some embodiments, R¹⁵ is NO₂. In some embodiments, R¹⁵ is COOR. In some embodiments, R¹⁵ is CHO. In some embodiments, R¹⁵ is CH₂OH. In some embodiments, R¹⁵ is OH. In some embodiments, R¹⁵ is OR. In some embodiments, R¹⁵ is SH. In some embodiments, R¹⁵ is SR. In some embodiments, R¹⁵ is C(O)N(R)₂. In some embodiments, R¹⁵ is C(O)NHR. In some embodiments, R¹⁵ is C(O)NH₂. In some embodiments, R¹⁵ is halide. In some embodiments, R¹⁵ is tosylate. In some embodiments, R¹⁵ is mesylate. In some embodiments, R¹⁵ is SO₂NHR. In some embodiments, R¹⁵ is triflate. In some embodiments, R¹⁵ is isocyanate. In some embodiments, R¹⁵ is cyanate. In some embodiments, R¹⁵ is thiocyanate. In some embodiments, R¹⁵ is isothiocyanate. In some embodiments, R¹⁵ is R. In some embodiments, R¹⁵ is cyano. In some embodiments, R¹⁵ is CF₃. In some embodiments, R¹⁵ is Si(OR)₃.

In some embodiments, R¹⁶ is CO₂H, CO₂M¹, CO₂R, SO₃H, SO₃M¹, PO₃H₂, PO₃M¹ _(2.) PO₃M¹H, PO₄H₂, PO₄M¹ ₂, PO₄M¹H, PO₄M², C(O)NHOH, NH₂, NHR, N(R)₂, NO₂, COOR, CHO, CH₂OH, OH, OR, SH, SR, C(O)N(R)₂, C(O)NHR, C(O)NH₂, halide, tosylate, mesylate, SO₂NHR, triflate, isocyanate, cyanate, thiocyanate, isothiocyanate, R, cyano CF₃ or Si(OR)₃. In some embodiments, R¹⁶ is CO₂H. In some embodiments, R¹⁶ is CO₂M¹. In some embodiments, R¹⁶ is CO₂R. In some embodiments, R¹⁶ is SO₃H. In some embodiments, R¹⁶ is SO₃M¹. In some embodiments, R¹⁶ is PO₃H₂. In some embodiments, R¹⁶ is PO₃M¹ ₂. In some embodiments, R¹⁶ is PO₃M¹H. In some embodiments, R¹⁶ is PO₄H₂. In some embodiments, R¹⁶ is PO₄M¹ ₂. In some embodiments, R¹⁶ is PO₄M¹H. In some embodiments, R¹⁶ is PO₄M². In some embodiments, R¹⁶ is C(O)NHOH. In some embodiments, R¹⁶ is NH₂. In some embodiments, R¹⁶ is NHR. In some embodiments, R¹⁶ is N(R)₂. In some embodiments, R¹⁶ is NO₂. In some embodiments, R¹⁶ is COOR. In some embodiments, R¹⁶ is CHO. In some embodiments, R¹⁶ is CH₂OH. In some embodiments, R¹⁶ is OH. In some embodiments, R¹⁶ is OR. In some embodiments, R¹⁶ is SH. In some embodiments, R¹⁶ is SR. In some embodiments, R¹⁶ is C(O)N(R)₂. In some embodiments, R¹⁶ is C(O)NHR. In some embodiments, R¹⁶ is C(O)NH₂. In some embodiments, R¹⁶ is halide. In some embodiments, R¹⁶ is tosylate. In some embodiments, R¹⁶ is mesylate. In some embodiments, R¹⁶ is SO₂NHR. In some embodiments, R¹⁶ is triflate. In some embodiments, R¹⁶ is isocyanate. In some embodiments, R¹⁶ is cyanate. In some embodiments, R¹⁶ is thiocyanate. In some embodiments, R¹⁶ is isothiocyanate. In some embodiments, R¹⁶ is R. In some embodiments, R¹⁶ is cyano. In some embodiments, R¹⁶ is CF₃. In some embodiments, R¹⁶ is Si(OR)₃.

In some embodiments, R¹⁷ is CO₂H, CO₂M¹, CO₂R, SO₃H, SO₃M¹, PO₃H₂, PO₃M¹ _(2.) PO₃M¹H, PO₄H₂, PO₄M¹ ₂, PO₄M¹H, PO₄M², C(O)NHOH, NH₂, NHR, N(R)₂, NO₂, COOR, CHO, CH₂OH, OH, OR, SH, SR, C(O)N(R)₂, C(O)NHR, C(O)NH₂, halide, tosylate, mesylate, SO₂NHR, triflate, isocyanate, cyanate, thiocyanate, isothiocyanate, R, cyano CF₃ or Si(OR)₃. In some embodiments, R¹⁷ is CO₂H. In some embodiments, R¹⁷ is CO₂M¹. In some embodiments, R¹⁷ is CO₂R. In some embodiments, R¹⁷ is SO₃H. In some embodiments, R¹⁷ is SO₃M¹. In some embodiments, R¹⁷ is PO₃H₂. In some embodiments, R¹⁷ is PO₃M¹ ₂. In some embodiments, R¹⁷ is PO₃M¹H. In some embodiments, R¹⁷ is PO₄H₂. In some embodiments, R¹⁷ is PO₄M¹ ₂. In some embodiments, R¹⁷ is PO₄M¹H. In some embodiments, R¹⁷ is PO₄M². In some embodiments, R¹⁷ is C(O)NHOH. In some embodiments, R¹⁷ is NH₂. In some embodiments, R¹⁷ is NHR. In some embodiments, R¹⁷ is N(R)₂. In some embodiments, R¹⁷ is NO₂. In some embodiments, R¹⁷ is COOR. In some embodiments, R¹⁷ is CHO. In some embodiments, R¹⁷ is CH₂OH. In some embodiments, R¹⁷ is OH. In some embodiments, R¹⁷ is OR. In some embodiments, R¹⁷ is SH. In some embodiments, R¹⁷ is SR. In some embodiments, R¹⁷ is C(O)N(R)₂. In some embodiments, R¹⁷ is C(O)NHR. In some embodiments, R¹⁷ is C(O)NH₂. In some embodiments, R¹⁷ is halide. In some embodiments, R¹⁷ is tosylate. In some embodiments, R¹⁷ is mesylate. In some embodiments, R¹⁷ is SO₂NHR. In some embodiments, R¹⁷ is triflate. In some embodiments, R¹⁷ is isocyanate. In some embodiments, R¹⁷ is cyanate. In some embodiments, R¹⁷ is thiocyanate. In some embodiments, R¹⁷ is isothiocyanate. In some embodiments, R¹⁷ is R. In some embodiments, R¹⁷ is cyano. In some embodiments, R¹⁷ is CF₃. In some embodiments, R¹⁷ is Si(OR)₃.

In some embodiments, R¹⁸ is CO₂H, CO₂M¹, CO₂R, SO₃H, SO₃M¹, PO₃H₂, PO₃M¹ _(2.) PO₃M¹H, PO₄H₂, PO₄M¹ ₂, PO₄M¹H, PO₄M², C(O)NHOH, NH₂, NHR, N(R)₂, NO₂, COOR, CHO, CH₂OH, OH, OR, SH, SR, C(O)N(R)₂, C(O)NHR, C(O)NH₂, halide, tosylate, mesylate, SO₂NHR, triflate, isocyanate, cyanate, thiocyanate, isothiocyanate, R, cyano CF₃ or Si(OR)₃. In some embodiments, R¹⁸ is CO₂H. In some embodiments, R¹⁸ is CO₂M¹. In some embodiments, R¹⁸ is CO₂R. In some embodiments, R¹⁸ is SO₃H. In some embodiments, R¹⁸ is SO₃M¹. In some embodiments, R¹⁸ is PO₃H₂. In some embodiments, R¹⁸ is PO₃M¹ ₂. In some embodiments, R¹⁸ is PO₃M¹H. In some embodiments, R¹⁸ is PO₄H₂. In some embodiments, R¹⁸ is PO₄M¹ ₂. In some embodiments, R¹⁸ is PO₄M¹H. In some embodiments, R¹⁸ is PO₄M². In some embodiments, R¹⁸ is C(O)NHOH. In some embodiments, R¹⁸ is NH₂. In some embodiments, R¹⁸ is NHR. In some embodiments, R¹⁸ is N(R)₂. In some embodiments, R¹⁸ is NO₂. In some embodiments, R¹⁸ is COOR. In some embodiments, R¹⁸ is CHO. In some embodiments, R¹⁸ is CH₂OH. In some embodiments, R¹⁸ is OH. In some embodiments, R¹⁸ is OR. In some embodiments, R¹³ is SH. In some embodiments, R¹⁸ is SR. In some embodiments, R¹⁸ is C(O)N(R)₂. In some embodiments, R¹⁸ is C(O)NHR. In some embodiments, R¹⁸ is C(O)NH₂. In some embodiments, R¹⁸ is halide. In some embodiments, R¹⁸ is tosylate. In some embodiments, R¹⁸ is mesylate. In some embodiments, R¹⁸ is SO₂NHR. In some embodiments, R¹⁸ is triflate. In some embodiments, R¹⁸ is isocyanate. In some embodiments, R¹⁸ is cyanate. In some embodiments, R¹⁸ is thiocyanate. In some embodiments, R¹⁸ is isothiocyanate. In some embodiments, R¹⁸ is R. In some embodiments, R¹⁸ is cyano. In some embodiments, R¹⁸ is CF₃. In some embodiments, R¹³ is Si(OR)₃.

In some embodiments, R¹⁹ is CO₂H, CO₂M¹, CO₂R, SO₃H, SO₃M¹, PO₃H₂, PO₃M¹ _(2.) PO₃M¹H, PO₄H₂, PO₄M¹ ₂, PO₄M¹H, PO₄M², C(O)NHOH, NH₂, NHR, N(R)₂, NO₂, COOR, CHO, CH₂OH, OH, OR, SH, SR, C(O)N(R)₂, C(O)NHR, C(O)NH₂, halide, tosylate, mesylate, SO₂NHR, triflate, isocyanate, cyanate, thiocyanate, isothiocyanate, R, cyano CF₃ or Si(OR)₃. In some embodiments, R¹⁹ is CO₂H. In some embodiments, R¹⁹ is CO₂M¹. In some embodiments, R¹⁹ is CO₂R. In some embodiments, R¹⁹ is SO₃H. In some embodiments, R¹⁹ is SO₃M¹. In some embodiments, R¹⁹ is PO₃H₂. In some embodiments, R¹⁹ is PO₃M¹ ₂. In some embodiments, R¹⁹ is PO₃M¹H. In some embodiments, R¹⁹ is PO₄H₂. In some embodiments, R¹⁹ is PO₄M¹ ₂. In some embodiments, R¹⁹ is PO₄M¹H. In some embodiments, R¹⁹ is PO₄M². In some embodiments, R¹⁹ is C(O)NHOH. In some embodiments, R¹⁹ is NH₂. In some embodiments, R¹⁹ is NHR. In some embodiments, R¹⁹ is N(R)₂. In some embodiments, R¹⁹ is NO₂. In some embodiments, R¹⁹ is COOR. In some embodiments, R¹⁹ is CHO. In some embodiments, R¹⁹ is CH₂OH. In some embodiments, R¹⁹ is OH. In some embodiments, R¹⁹ is OR. In some embodiments, R¹⁹ is SH. In some embodiments, R¹⁹ is SR. In some embodiments, R¹⁹ is C(O)N(R)₂. In some embodiments, R¹⁹ is C(O)NHR. In some embodiments, R¹⁹ is C(O)NH₂. In some embodiments, R¹⁹ is halide. In some embodiments, R¹⁹ is tosylate. In some embodiments, R¹⁹ is mesylate. In some embodiments, R¹⁹ is SO₂NHR. In some embodiments, R¹⁹ is triflate. In some embodiments, R¹⁹ is isocyanate. In some embodiments, R¹⁹ is cyanate. In some embodiments, R¹⁹ is thiocyanate. In some embodiments, R¹⁹ is isothiocyanate. In some embodiments, R¹⁹ is R. In some embodiments, R¹⁹ is cyano. In some embodiments, R¹⁹ is CF₃. In some embodiments, R¹⁹ is Si(OR)₃.

In some embodiments, R²⁰ is CO₂H, CO₂M¹, CO₂R, SO₃H, SO₃M¹, PO₃H₂, PO₃M¹ _(2.) PO₃M¹H, PO₄H₂, PO₄M¹ ₂, PO₄M¹H, PO₄M², C(O)NHOH, NH₂, NHR, N(R)₂, NO₂, COOR, CHO, CH₂OH, OH, OR, SH, SR, C(O)N(R)₂, C(O)NHR, C(O)NH₂, halide, tosylate, mesylate, SO₂NHR, triflate, isocyanate, cyanate, thiocyanate, isothiocyanate, R, cyano CF₃ or Si(OR)₃. In some embodiments, R²⁰ is CO₂H. In some embodiments, R²⁰ is CO₂M¹. In some embodiments, R²⁰ is CO₂R. In some embodiments, R²⁰ is SO₃H. In some embodiments, R²⁰ is SO₃M¹. In some embodiments, R²⁰ is PO₃H₂. In some embodiments, R²⁰ is PO₃M¹ ₂. In some embodiments, R²⁰ is PO₃M¹H. In some embodiments, R²⁰ is PO₄H₂. In some embodiments, R²⁰ is PO₄M¹ ₂. In some embodiments, R²⁰ is PO₄M¹H. In some embodiments, R²⁰ is PO₄M². In some embodiments, R²⁰ is C(O)NHOH. In some embodiments, R²⁰ is NH₂. In some embodiments, R²⁰ is NHR. In some embodiments, R²⁰ is N(R)₂. In some embodiments, R²⁰ is NO₂. In some embodiments, R²⁰ is COOR. In some embodiments, R²⁰ is CHO. In some embodiments, R²⁰ is CH₂OH. In some embodiments, R²⁰ is OH. In some embodiments, R²⁰ is OR. In some embodiments, R¹³ is SH. In some embodiments, R²⁰ is SR. In some embodiments, R²⁰ is C(O)N(R)₂. In some embodiments, R²⁰ is C(O)NHR. In some embodiments, R²⁰ is C(O)NH₂. In some embodiments, R²⁰ is halide. In some embodiments, R²⁰ is tosylate. In some embodiments, R²⁰ is mesylate. In some embodiments, R²⁰ is SO₂NHR. In some embodiments, R²⁰ is triflate. In some embodiments, R²⁰ is isocyanate. In some embodiments, R²⁰ is cyanate. In some embodiments, R²⁰ is thiocyanate. In some embodiments, R²⁰ is isothiocyanate. In some embodiments, R²⁰ is R. In some embodiments, R²⁰ is cyano. In some embodiments, R²⁰ is CF₃. In some embodiments, R²⁰ is Si(OR)₃.

In some embodiments, R²¹ is CO₂H, CO₂M¹, CO₂R, SO₃H, SO₃M¹, PO₃H₂, PO₃M¹ _(2.) PO₃M¹H, PO₄H₂, PO₄M¹ ₂, PO₄M¹H, PO₄M², C(O)NHOH, NH₂, NHR, N(R)₂, NO₂, COOR, CHO, CH₂OH, OH, OR, SH, SR, C(O)N(R)₂, C(O)NHR, C(O)NH₂, halide, tosylate, mesylate, SO₂NHR, triflate, isocyanate, cyanate, thiocyanate, isothiocyanate, R, cyano CF₃ or Si(OR)₃. In some embodiments, R²¹ is CO₂H. In some embodiments, R²¹ is CO₂M¹. In some embodiments, R²¹ is CO₂R. In some embodiments, R²¹ is SO₃H. In some embodiments, R²¹ is SO₃M¹. In some embodiments, R²¹ is PO₃H₂. In some embodiments, R²¹ is PO₃M¹ ₂. In some embodiments, R²¹ is PO₃M¹H. In some embodiments, R²¹ is PO₄H₂. In some embodiments, R²¹ is PO₄M¹ ₂. In some embodiments, R²¹ is PO₄M¹H. In some embodiments, R²¹ is PO₄M². In some embodiments, R²¹ is C(O)NHOH. In some embodiments, R²¹ is NH₂. In some embodiments, R²¹ is NHR. In some embodiments, R²¹ is N(R)₂. In some embodiments, R²¹ is NO₂. In some embodiments, R²¹ is COOR. In some embodiments, R²¹ is CHO. In some embodiments, R²¹ is CH₂OH. In some embodiments, R²¹ is OH. In some embodiments, R²¹ is OR. In some embodiments, R¹³ is SH. In some embodiments, R²¹ is SR. In some embodiments, R²¹ is C(O)N(R)₂. In some embodiments, R²¹ is C(O)NHR. In some embodiments, R²¹ is C(O)NH₂. In some embodiments, R²¹ is halide. In some embodiments, R²¹ is tosylate. In some embodiments, R²¹ is mesylate. In some embodiments, R²¹ is SO₂NHR. In some embodiments, R²¹ is triflate. In some embodiments, R²¹ is isocyanate. In some embodiments, R²¹ is cyanate. In some embodiments, R²¹ is thiocyanate. In some embodiments, R²¹ is isothiocyanate. In some embodiments, R²¹ is R. In some embodiments, R²¹ is cyano. In some embodiments, R²¹ is CF₃. In some embodiments, R²¹ is Si(OR)₃.

In some embodiments, R²² is CO₂H, CO₂M¹, CO₂R, SO₃H, SO₃M¹, PO₃H₂, PO₃M¹ _(2.) PO₃M¹H, PO₄H₂, PO₄M¹ ₂, PO₄M¹H, PO₄M², C(O)NHOH, NH₂, NHR, N(R)₂, NO₂, COOR, CHO, CH₂OH, OH, OR, SH, SR, C(O)N(R)₂, C(O)NHR, C(O)NH₂, halide, tosylate, mesylate, SO₂NHR, triflate, isocyanate, cyanate, thiocyanate, isothiocyanate, R, cyano CF₃ or Si(OR)₃. In some embodiments, R²² is CO₂H. In some embodiments, R²² is CO₂M¹. In some embodiments, R²² is CO₂R. In some embodiments, R²² is SO₃H. In some embodiments, R²² is SO₃M¹. In some embodiments, R²² is PO₃H₂. In some embodiments, R²² is PO₃M¹ ₂. In some embodiments, R²² is PO₃M¹H. In some embodiments, R²² is PO₄H₂. In some embodiments, R²² is PO₄M¹ ₂. In some embodiments, R²² is PO₄M¹H. In some embodiments, R²² is PO₄M². In some embodiments, R²² is C(O)NHOH. In some embodiments, R²² is NH₂. In some embodiments, R²² is NHR. In some embodiments, R²² is N(R)₂. In some embodiments, R²² is NO₂. In some embodiments, R²² is COOR. In some embodiments, R²² is CHO. In some embodiments, R²² is CH₂OH. In some embodiments, R²² is OH. In some embodiments, R²² is OR. In some embodiments, R²² is SH. In some embodiments, R²² is SR. In some embodiments, R²² is C(O)N(R)₂. In some embodiments, R²² is C(O)NHR. In some embodiments, R²² is C(O)NH₂. In some embodiments, R²² is halide. In some embodiments, R²² is tosylate. In some embodiments, R²² is mesylate. In some embodiments, R²² is SO₂NHR. In some embodiments, R²² is triflate. In some embodiments, R²² is isocyanate. In some embodiments, R²² is cyanate. In some embodiments, R²² is thiocyanate. In some embodiments, R²² is isothiocyanate. In some embodiments, R²² is R. In some embodiments, R²² is cyano. In some embodiments, R²² is CF₃. In some embodiments, R²² is Si(OR)₃.

In some embodiments, R¹⁰¹ is CO₂H, CO₂M¹, CO₂R, SO₃H, SO₃M¹, PO₃H₂, PO₃M¹ _(2.) PO₃M¹H, PO₄H₂, PO₄M¹ ₂, PO₄M¹H, PO₄M², C(O)NHOH, NH₂, NHR, N(R)₂, NO₂, COOR, CHO, CH₂OH, OH, OR, SH, SR, C(O)N(R)₂, C(O)NHR, C(O)NH₂, halide, tosylate, mesylate, SO₂NHR, triflate, isocyanate, cyanate, thiocyanate, isothiocyanate, R, cyano CF₃ or Si(OR)₃. In some embodiments, R¹⁰¹ is CO₂H. In some embodiments, R¹⁰¹ is CO₂M¹. In some embodiments, R¹⁰¹ is CO₂R. In some embodiments, R¹⁰¹ is SO₃H. In some embodiments, R¹⁰¹ is SO₃M¹. In some embodiments, R¹⁰¹ is PO₃H₂. In some embodiments, R¹⁰¹ is PO₃M¹ ₂. In some embodiments, R¹⁰¹ is PO₃M¹H. In some embodiments, R¹⁰¹ is PO₄H₂. In some embodiments, R¹⁰¹ is PO₄M¹ ₂. In some embodiments, R¹⁰¹ is PO₄M¹H. In some embodiments, R¹⁰¹ is PO₄M². In some embodiments, R¹⁰¹ is C(O)NHOH. In some embodiments, R¹⁰¹ is NH₂. In some embodiments, R¹⁰¹ is NHR. In some embodiments, R¹⁰¹ is N(R)₂. In some embodiments, R¹⁰¹ is NO₂. In some embodiments, R¹⁰¹ is COOR. In some embodiments, R¹⁰¹ is CHO. In some embodiments, R¹⁰¹ is CH₂OH. In some embodiments, R¹⁰¹ is OH. In some embodiments, R¹⁰¹ is OR. In some embodiments, R¹⁰¹ is SH. In some embodiments, R¹⁰¹ is SR. In some embodiments, R¹⁰¹ is C(O)N(R)₂. In some embodiments, R¹⁰¹ is C(O)NHR. In some embodiments, R¹⁰¹ is C(O)NH₂. In some embodiments, R¹⁰¹ is halide. In some embodiments, R¹⁰¹ is tosylate. In some embodiments, R¹⁰¹ is mesylate. In some embodiments, R¹⁰¹ is SO₂NHR. In some embodiments, R¹⁰¹ is triflate. In some embodiments, R¹⁰¹ is isocyanate. In some embodiments, R¹⁰¹ is cyanate. In some embodiments, R¹⁰¹ is thiocyanate. In some embodiments, R¹⁰¹ is isothiocyanate. In some embodiments, R¹⁰¹ is R. In some embodiments, R¹⁰¹ is cyano. In some embodiments, R¹⁰¹ is CF₃. In some embodiments, R¹⁰¹ is Si(OR)₃.

In some embodiments, R¹⁰² is CO₂H, CO₂M¹, CO₂R, SO₃H, SO₃M¹, PO₃H₂, PO₃M¹ _(2.) PO₃M¹H, PO₄H₂, PO₄M¹ ₂, PO₄M¹H, PO₄M², C(O)NHOH, NH₂, NHR, N(R)₂, NO₂, COOR, CHO, CH₂OH, OH, OR, SH, SR, C(O)N(R)₂, C(O)NHR, C(O)NH₂, halide, tosylate, mesylate, SO₂NHR, triflate, isocyanate, cyanate, thiocyanate, isothiocyanate, R, cyano CF₃ or Si(OR)₃. In some embodiments, R¹⁰² is CO₂H. In some embodiments, R¹⁰² is CO₂M¹. In some embodiments, R¹⁰² is CO₂R. In some embodiments, R¹⁰² is SO₃H. In some embodiments, R¹⁰² is SO₃M¹. In some embodiments, R¹⁰² is PO₃H₂. In some embodiments, R¹⁰² is PO₃M¹ ₂. In some embodiments, R¹⁰² is PO₃M¹H. In some embodiments, R¹⁰² is PO₄H₂. In some embodiments, R¹⁰² is PO₄M¹ ₂. In some embodiments, R¹⁰² is PO₄M¹H. In some embodiments, R¹⁰² is PO₄M². In some embodiments, R¹⁰² is C(O)NHOH. In some embodiments, R¹⁰² is NH₂. In some embodiments, R¹⁰² is NHR. In some embodiments, R¹⁰² is N(R)₂. In some embodiments, R¹⁰² is NO₂. In some embodiments, R¹⁰² is COOR. In some embodiments, R¹⁰² is CHO. In some embodiments, R¹⁰² is CH₂OH. In some embodiments, R¹⁰² is OH. In some embodiments, R¹⁰² is OR. In some embodiments, R¹⁰² is SH. In some embodiments, R¹⁰² is SR. In some embodiments, R¹⁰² is C(O)N(R)₂. In some embodiments, R¹⁰² is C(O)NHR. In some embodiments, R¹⁰² is C(O)NH₂. In some embodiments, R¹⁰² is halide. In some embodiments, R¹⁰² is tosylate. In some embodiments, R¹⁰² is mesylate. In some embodiments, R¹⁰² is SO₂NHR. In some embodiments, R¹⁰² is triflate. In some embodiments, R¹⁰² is isocyanate. In some embodiments, R¹⁰² is cyanate. In some embodiments, R¹⁰² is thiocyanate. In some embodiments, R¹⁰² is isothiocyanate. In some embodiments, R¹⁰² is R. In some embodiments, R¹⁰² is cyano. In some embodiments, R¹⁰² is CF₃. In some embodiments, R¹⁰² is Si(OR)₃.

In some embodiments, R¹⁰⁴ is CO₂H, CO₂M¹, CO₂R, SO₃H, SO₃M¹, PO₃H₂, PO₃M¹ _(2.) PO₃M¹H, PO₄H₂, PO₄M¹ ₂, PO₄M¹H, PO₄M², C(O)NHOH, NH₂, NHR, N(R)₂, NO₂, COOR, CHO, CH₂OH, OH, OR, SH, SR, C(O)N(R)₂, C(O)NHR, C(O)NH₂, halide, tosylate, mesylate, SO₂NHR, triflate, isocyanate, cyanate, thiocyanate, isothiocyanate, R, cyano CF₃ or Si(OR)₃. In some embodiments, R¹⁰⁴ is CO₂H. In some embodiments, R¹⁰⁴ is CO₂M¹. In some embodiments, R¹⁰⁴ is CO₂R. In some embodiments, R¹⁰⁴ is SO₃H. In some embodiments, R¹⁰⁴ is SO₃M¹. In some embodiments, R¹⁰⁴ is PO₃H₂. In some embodiments, R¹⁰⁴ is PO₃M¹ ₂. In some embodiments, R¹⁰⁴ is PO₃M¹H. In some embodiments, R¹⁰⁴ is PO₄H₂. In some embodiments, R¹⁰⁴ is PO₄M¹ ₂. In some embodiments, R¹⁰⁴ is PO₄M¹H. In some embodiments, R¹⁰⁴ is PO₄M². In some embodiments, R¹⁰⁴ is C(O)NHOH. In some embodiments, R¹⁰⁴ is NH₂. In some embodiments, R¹⁰⁴ is NHR. In some embodiments, R¹⁰⁴ is N(R)₂. In some embodiments, R¹⁰⁴ is NO₂. In some embodiments, R¹⁰⁴ is COOR. In some embodiments, R¹⁰⁴ is CHO. In some embodiments, R¹⁰⁴ is CH₂OH. In some embodiments, R¹⁰⁴ is OH. In some embodiments, R¹⁰⁴ is OR. In some embodiments, R¹⁰⁴ is SH. In some embodiments, R¹⁰⁴ is SR. In some embodiments, R¹⁰⁴ is C(O)N(R)₂. In some embodiments, R¹⁰⁴ is C(O)NHR. In some embodiments, R¹⁰⁴ is C(O)NH₂. In some embodiments, R¹⁰⁴ is halide. In some embodiments, R¹⁰⁴ is tosylate. In some embodiments, R¹⁰⁴ is mesylate. In some embodiments, R¹⁰⁴ is SO₂NHR. In some embodiments, R¹⁰⁴ is triflate. In some embodiments, R¹⁰⁴ is isocyanate. In some embodiments, R¹⁰⁴ is cyanate. In some embodiments, R¹⁰⁴ is thiocyanate. In some embodiments, R¹⁰⁴ is isothiocyanate. In some embodiments, R¹⁰⁴ is R. In some embodiments, R¹⁰⁴ is cyano. In some embodiments, R¹⁰⁴ is CF₃. In some embodiments, R¹⁰⁴ is Si(OR)₃.

In some embodiments, R¹⁰⁵ is CO₂H, CO₂M¹, CO₂R, SO₃H, SO₃M¹, PO₃H₂, PO₃M¹ _(2.) PO₃M¹H, PO₄H₂, PO₄M¹ ₂, PO₄M¹H, PO₄M², C(O)NHOH, NH₂, NHR, N(R)₂, NO₂, COOR, CHO, CH₂OH, OH, OR, SH, SR, C(O)N(R)₂, C(O)NHR, C(O)NH₂, halide, tosylate, mesylate, SO₂NHR, triflate, isocyanate, cyanate, thiocyanate, isothiocyanate, R, cyano CF₃ or Si(OR)₃. In some embodiments, R¹⁰⁵ is CO₂H. In some embodiments, R¹⁰⁵ is CO₂M¹. In some embodiments, R¹⁰⁵ is CO₂R. In some embodiments, R¹⁰⁵ is SO₃H. In some embodiments, R¹⁰⁵ is SO₃M¹. In some embodiments, R¹⁰⁵ is PO₃H₂. In some embodiments, R¹⁰⁵ is PO₃M¹ ₂. In some embodiments, R¹⁰⁵ is PO₃M¹H. In some embodiments, R¹⁰⁵ is PO₄H₂. In some embodiments, R¹⁰⁵ is PO₄M¹ ₂. In some embodiments, R¹⁰⁵ is PO₄M¹H. In some embodiments, R¹⁰⁵ is PO₄M². In some embodiments, R¹⁰⁵ is C(O)NHOH. In some embodiments, R¹⁰⁵ is NH₂. In some embodiments, R¹⁰⁵ is NHR. In some embodiments, R¹⁰⁵ is N(R)₂. In some embodiments, R¹⁰⁵ is NO₂. In some embodiments, R¹⁰⁵ is COOR. In some embodiments, R¹⁰⁵ is CHO. In some embodiments, R¹⁰⁵ is CH₂OH. In some embodiments, R¹⁰⁵ is OH. In some embodiments, R¹⁰⁵ is OR. In some embodiments, R¹⁰⁵ is SH. In some embodiments, R¹⁰⁵ is SR. In some embodiments, R¹⁰⁵ is C(O)N(R)₂. In some embodiments, R¹⁰⁵ is C(O)NHR. In some embodiments, R¹⁰⁵ is C(O)NH₂. In some embodiments, R¹⁰⁵ is halide. In some embodiments, R¹⁰⁵ is tosylate. In some embodiments, R¹⁰⁵ is mesylate. In some embodiments, R¹⁰⁵ is SO₂NHR. In some embodiments, R¹⁰⁵ is triflate. In some embodiments, R¹⁰⁵ is isocyanate. In some embodiments, R¹⁰⁵ is cyanate. In some embodiments, R¹⁰⁵ is thiocyanate. In some embodiments, R¹⁰⁵ is isothiocyanate. In some embodiments, R¹⁰⁵ is R. In some embodiments, R¹⁰⁵ is cyano. In some embodiments, R¹⁰⁵ is CF₃. In some embodiments, R¹⁰⁵ is Si(OR)₃.

In some embodiments, R¹⁰⁶ is CO₂H, CO₂M¹, CO₂R, SO₃H, SO₃M¹, PO₃H₂, PO₃M¹ _(2.) PO₃M¹H, PO₄H₂, PO₄M¹ ₂, PO₄M¹H, PO₄M², C(O)NHOH, NH₂, NHR, N(R)₂, NO₂, COOR, CHO, CH₂OH, OH, OR, SH, SR, C(O)N(R)₂, C(O)NHR, C(O)NH₂, halide, tosylate, mesylate, SO₂NHR, triflate, isocyanate, cyanate, thiocyanate, isothiocyanate, R, cyano CF₃ or Si(OR)₃. In some embodiments, R¹⁰⁶ is CO₂H. In some embodiments, R¹⁰⁶ is CO₂M¹. In some embodiments, R¹⁰⁶ is CO₂R. In some embodiments, R¹⁰⁶ is SO₃H. In some embodiments, R¹⁰⁶ is SO₃M¹. In some embodiments, R¹⁰⁶ is PO₃H₂. In some embodiments, R¹⁰⁶ is PO₃M¹ ₂. In some embodiments, R¹⁰⁶ is PO₃M¹H. In some embodiments, R¹⁰⁶ is PO₄H₂. In some embodiments, R¹⁰⁶ is PO₄M¹ ₂. In some embodiments, R¹⁰⁶ is PO₄M¹H. In some embodiments, R¹⁰⁶ is PO₄M². In some embodiments, R¹⁰⁶ is C(O)NHOH. In some embodiments, R¹⁰⁶ is NH₂. In some embodiments, R¹⁰⁶ is NHR. In some embodiments, R¹⁰⁶ is N(R)₂. In some embodiments, R¹⁰⁶ is NO₂. In some embodiments, R¹⁰⁶ is COOR. In some embodiments, R¹⁰⁶ is CHO. In some embodiments, R¹⁰⁶ is CH₂OH. In some embodiments, R¹⁰⁶ is OH. In some embodiments, R¹⁰⁶ is OR. In some embodiments, R¹⁰⁶ is SH. In some embodiments, R¹⁰⁶ is SR. In some embodiments, R¹⁰⁶ is C(O)N(R)₂. In some embodiments, R¹⁰⁶ is C(O)NHR. In some embodiments, R¹⁰⁶ is C(O)NH₂. In some embodiments, R¹⁰⁶ is halide. In some embodiments, R¹⁰⁶ is tosylate. In some embodiments, R¹⁰⁶ is mesylate. In some embodiments, R¹⁰⁶ is SO₂NHR. In some embodiments, R¹⁰⁶ is triflate. In some embodiments, R¹⁰⁶ is isocyanate. In some embodiments, R¹⁰⁶ is cyanate. In some embodiments, R¹⁰⁶ is thiocyanate. In some embodiments, R¹⁰⁶ is isothiocyanate. In some embodiments, R¹⁰⁶ is R. In some embodiments, R¹⁰⁶ is cyano. In some embodiments, R¹⁰⁶ is CF₃. In some embodiments, R¹⁰⁶ is Si(OR)₃.

In some embodiments, T¹ is H, CO₂H, CO₂M¹, CO₂R, SO₃H, SO₃M¹, PO₃H₂, PO₃M¹ _(2.) PO₃M¹H, PO₄H₂, PO₄M¹ ₂, PO₄M¹H, PO₄M², C(O)NHOH, NH₂, NHR, N(R)₂, NO₂, COOR, CHO, CH₂OH, OH, OR, SH, SR, C(O)N(R)₂, C(O)NHR, C(O)NH₂, halide, tosylate, mesylate, SO₂NHR, triflate, isocyanate, cyanate, thiocyanate, isothiocyanate, R, cyano CF₃ or Si(OR)₃. In some embodiments, T² is H. In some embodiments, T¹ is CO₂H. In some embodiments, T¹ is CO₂M¹. In some embodiments, T¹ is CO₂R. In some embodiments, T¹ is SO₃H. In some embodiments, T¹ is SO₃M¹. In some embodiments, T¹ is PO₃H₂. In some embodiments, T¹ is PO₃M¹ ₂. In some embodiments, T¹ is PO₃M¹H. In some embodiments, T¹ is PO₄H₂. In some embodiments, T¹ is PO₄M¹ ₂. In some embodiments, T¹ is PO₄M¹H. In some embodiments, T¹ is PO₄M². In some embodiments, T¹ is C(O)NHOH. In some embodiments, T¹ is NH₂. In some embodiments, T¹ is NHR. In some embodiments, T¹ is N(R)₂. In some embodiments, T¹ is NO₂. In some embodiments, T¹ is COOR. In some embodiments, T¹ is CHO. In some embodiments, T¹ is CH₂OH. In some embodiments, T¹ is OH. In some embodiments, T¹ is OR. In some embodiments, T¹ is SH. In some embodiments, T¹ is SR. In some embodiments, T¹ is C(O)N(R)₂. In some embodiments, T¹ is C(O)NHR. In some embodiments, T¹ is C(O)NH₂. In some embodiments, T¹ is halide. In some embodiments, T¹ is tosylate. In some embodiments, T¹ is mesylate. In some embodiments, T¹ is SO₂NHR. In some embodiments, T¹ is triflate. In some embodiments, T¹ is isocyanate. In some embodiments, T¹ is cyanate. In some embodiments, T¹ is thiocyanate. In some embodiments, T¹ is isothiocyanate. In some embodiments, T¹ is R. In some embodiments, T¹ is cyano. In some embodiments, T¹ is CF₃. In some embodiments, T¹ is Si(OR)₃.

In some embodiments, T² is H, CO₂H, CO₂M¹, CO₂R, SO₃H, SO₃M¹, PO₃H₂, PO₃M¹ _(2.) PO₃M¹H, PO₄H₂, PO₄M¹ ₂, PO₄M¹H, PO₄M², C(O)NHOH, NH₂, NHR, N(R)₂, NO₂, COOR, CHO, CH₂OH, OH, OR, SH, SR, C(O)N(R)₂, C(O)NHR, C(O)NH₂, halide, tosylate, mesylate, SO₂NHR, triflate, isocyanate, cyanate, thiocyanate, isothiocyanate, R, cyano CF₃ or Si(OR)₃. In some embodiments, T² is H. In some embodiments, T² is CO₂H. In some embodiments, T² is CO₂M¹. In some embodiments, T² is CO₂R. In some embodiments, T² is SO₃H. In some embodiments, T² is SO₃M¹. In some embodiments, T² is PO₃H₂. In some embodiments, T² is PO₃M¹ ₂. In some embodiments, T² is PO₃M¹H. In some embodiments, T² is PO₄H₂. In some embodiments, T² is PO₄M¹ ₂. In some embodiments, T² is PO₄M¹H. In some embodiments, T² is PO₄M². In some embodiments, T² is C(O)NHOH. In some embodiments, T² is NH₂. In some embodiments, T² is NHR. In some embodiments, T² is N(R)₂. In some embodiments, T² is NO₂. In some embodiments, T² is COOR. In some embodiments, T² is CHO. In some embodiments, T² is CH₂OH. In some embodiments, T² is OH. In some embodiments, T² is OR. In some embodiments, T² is SH. In some embodiments, T² is SR. In some embodiments, T² is C(O)N(R)₂. In some embodiments, T² is C(O)NHR. In some embodiments, T² is C(O)NH₂. In some embodiments, T² is halide. In some embodiments, T² is tosylate. In some embodiments, T² is mesylate. In some embodiments, T² is SO₂NHR. In some embodiments, T² is triflate. In some embodiments, T² is isocyanate. In some embodiments, T² is cyanate. In some embodiments, T² is thiocyanate. In some embodiments, T² is isothiocyanate. In some embodiments, T² is R. In some embodiments, T² is cyano. In some embodiments, T² is CF₃. In some embodiments, T² is Si(OR)₃.

In some embodiments, T³ is H, CO₂H, CO₂M¹, CO₂R, SO₃H, SO₃M¹, PO₃H₂, PO₃M¹ _(2.) PO₃M¹H, PO₄H₂, PO₄M¹ ₂, PO₄M¹H, PO₄M², C(O)NHOH, NH₂, NHR, N(R)₂, NO₂, COOR, CHO, CH₂OH, OH, OR, SH, SR, C(O)N(R)₂, C(O)NHR, C(O)NH₂, halide, tosylate, mesylate, SO₂NHR, triflate, isocyanate, cyanate, thiocyanate, isothiocyanate, R, cyano CF₃ or Si(OR)₃. In some embodiments, T³ is H. In some embodiments, T³ is CO₂H. In some embodiments, T³ is CO₂M¹. In some embodiments, T³ is CO₂R. In some embodiments, T³ is SO₃H. In some embodiments, T³ is SO₃M¹. In some embodiments, T³ is PO₃H₂. In some embodiments, T³ is PO₃M¹ ₂. In some embodiments, T³ is PO₃M¹H. In some embodiments, T³ is PO₄H₂. In some embodiments, T³ is PO₄M¹ ₂. In some embodiments, T³ is PO₄M¹H. In some embodiments, T³ is PO₄M². In some embodiments, T³ is C(O)NHOH. In some embodiments, T³ is NH₂. In some embodiments, T³ is NHR. In some embodiments, T³ is N(R)₂. In some embodiments, T³ is NO₂. In some embodiments, T³ is COOR. In some embodiments, T³ is CHO. In some embodiments, T³ is CH₂OH. In some embodiments, T³ is OH. In some embodiments, T³ is OR. In some embodiments, T³ is SH. In some embodiments, T³ is SR. In some embodiments, T³ is C(O)N(R)₂. In some embodiments, T³ is C(O)NHR. In some embodiments, T³ is C(O)NH₂. In some embodiments, T³ is halide. In some embodiments, T³ is tosylate. In some embodiments, T³ is mesylate. In some embodiments, T³ is SO₂NHR. In some embodiments, T³ is triflate. In some embodiments, T³ is isocyanate. In some embodiments, T³ is cyanate. In some embodiments, T³ is thiocyanate. In some embodiments, T³ is isothiocyanate. In some embodiments, T³ is R. In some embodiments, T³ is cyano. In some embodiments, T³ is CF₃. In some embodiments, T³ is Si(OR)₃.

In some embodiments, T⁴ is H, CO₂H, CO₂M¹, CO₂R, SO₃H, SO₃M¹, PO₃H₂, PO₃M¹ _(2.) PO₃M¹H, PO₄H₂, PO₄M¹ ₂, PO₄M¹H, PO₄M², C(O)NHOH, NH₂, NHR, N(R)₂, NO₂, COOR, CHO, CH₂OH, OH, OR, SH, SR, C(O)N(R)₂, C(O)NHR, C(O)NH₂, halide, tosylate, mesylate, SO₂NHR, triflate, isocyanate, cyanate, thiocyanate, isothiocyanate, R, cyano CF₃ or Si(OR)₃. In some embodiments, T⁴ is H. In some embodiments, T⁴ is CO₂H. In some embodiments, T⁴ is CO₂M¹. In some embodiments, T⁴ is CO₂R. In some embodiments, T⁴ is SO₃H. In some embodiments, T⁴ is SO₃M¹. In some embodiments, T⁴ is PO₃H₂. In some embodiments, T⁴ is PO₃M¹ ₂. In some embodiments, T⁴ is PO₃M¹H. In some embodiments, T⁴ is PO₄H₂. In some embodiments, T⁴ is PO₄M¹ ₂. In some embodiments, T⁴ is PO₄M¹H. In some embodiments, T⁴ is PO₄M². In some embodiments, T⁴ is C(O)NHOH. In some embodiments, T⁴ is NH₂. In some embodiments, T⁴ is NHR. In some embodiments, T⁴ is N(R)₂. In some embodiments, T⁴ is NO₂. In some embodiments, T⁴ is COOR. In some embodiments, T⁴ is CHO. In some embodiments, T⁴ is CH₂OH. In some embodiments, T⁴ is OH. In some embodiments, T⁴ is OR. In some embodiments, T³ is SH. In some embodiments, T⁴ is SR. In some embodiments, T⁴ is C(O)N(R)₂. In some embodiments, T⁴ is C(O)NHR. In some embodiments, T⁴ is C(O)NH₂. In some embodiments, T⁴ is halide. In some embodiments, T⁴ is tosylate. In some embodiments, T⁴ is mesylate. In some embodiments, T⁴ is SO₂NHR. In some embodiments, T⁴ is triflate. In some embodiments, T⁴ is isocyanate. In some embodiments, T⁴ is cyanate. In some embodiments, T⁴ is thiocyanate. In some embodiments, T⁴ is isothiocyanate. In some embodiments, T⁴ is R. In some embodiments, T⁴ is cyano. In some embodiments, T⁴ is CF₃. In some embodiments, T⁴ is Si(OR)₃.

In some embodiments, T⁵ is H, CO₂H, CO₂M¹, CO₂R, SO₃H, SO₃M¹, PO₃H₂, PO₃M¹ _(2.) PO₃M¹H, PO₄H₂, PO₄M¹ ₂, PO₄M¹H, PO₄M², C(O)NHOH, NH₂, NHR, N(R)₂, NO₂, COOR, CHO, CH₂OH, OH, OR, SH, SR, C(O)N(R)₂, C(O)NHR, C(O)NH₂, halide, tosylate, mesylate, SO₂NHR, triflate, isocyanate, cyanate, thiocyanate, isothiocyanate, R, cyano CF₃ or Si(OR)₃. In some embodiments, T⁵ is H. In some embodiments, T⁵ is CO₂H. In some embodiments, T⁵ is CO₂M¹. In some embodiments, T⁵ is CO₂R. In some embodiments, T⁵ is SO₃H. In some embodiments, T⁵ is SO₃M¹. In some embodiments, T⁵ is PO₃H₂. In some embodiments, T⁵ is PO₃M¹ ₂. In some embodiments, T⁵ is PO₃M¹H. In some embodiments, T⁵ is PO₄H₂. In some embodiments, T⁵ is PO₄M¹ ₂. In some embodiments, T⁵ is PO₄M¹H. In some embodiments, T⁵ is PO₄M². In some embodiments, T⁵ is C(O)NHOH. In some embodiments, T⁵ is NH₂. In some embodiments, T⁵ is NHR. In some embodiments, T⁵ is N(R)₂. In some embodiments, T⁵ is NO₂. In some embodiments, T⁵ is COOR. In some embodiments, T⁵ is CHO. In some embodiments, T⁵ is CH₂OH. In some embodiments, T⁵ is OH. In some embodiments, T⁵ is OR. In some embodiments, T⁵ is SH. In some embodiments, T⁵ is SR. In some embodiments, T⁵ is C(O)N(R)₂. In some embodiments, T⁵ is C(O)NHR. In some embodiments, T⁵ is C(O)NH₂. In some embodiments, T⁵ is halide. In some embodiments, T⁵ is tosylate. In some embodiments, T⁵ is mesylate. In some embodiments, T⁵ is SO₂NHR. In some embodiments, T⁵ is triflate. In some embodiments, T⁵ is isocyanate. In some embodiments, T⁵ is cyanate. In some embodiments, T⁵ is thiocyanate. In some embodiments, T⁵ is isothiocyanate. In some embodiments, T⁵ is R. In some embodiments, T⁵ is cyano. In some embodiments, T⁵ is CF₃. In some embodiments, T⁵ is Si(OR)₃.

In some embodiments, T⁶ is H, CO₂H, CO₂M¹, CO₂R, SO₃H, SO₃M¹, PO₃H₂, PO₃M¹ _(2.) PO₃M¹H, PO₄H₂, PO₄M¹ ₂, PO₄M¹H, PO₄M², C(O)NHOH, NH₂, NHR, N(R)₂, NO₂, COOR, CHO, CH₂OH, OH, OR, SH, SR, C(O)N(R)₂, C(O)NHR, C(O)NH₂, halide, tosylate, mesylate, SO₂NHR, triflate, isocyanate, cyanate, thiocyanate, isothiocyanate, R, cyano CF₃ or Si(OR)₃. In some embodiments, T⁶ is H. In some embodiments, T⁶ is CO₂H. In some embodiments, T⁶ is CO₂M¹. In some embodiments, T⁶ is CO₂R. In some embodiments, T⁶ is SO₃H. In some embodiments, T⁶ is SO₃M¹. In some embodiments, T⁶ is PO₃H₂. In some embodiments, T⁶ is PO₃M¹ ₂. In some embodiments, T⁶ is PO₃M¹H. In some embodiments, T⁶ is PO₄H₂. In some embodiments, T⁶ is PO₄M¹ ₂. In some embodiments, T⁶ is PO₄M¹H. In some embodiments, T⁶ is PO₄M². In some embodiments, T⁶ is C(O)NHOH. In some embodiments, T⁶ is NH₂. In some embodiments, T⁶ is NHR. In some embodiments, T⁶ is N(R)₂. In some embodiments, T⁶ is NO₂. In some embodiments, T⁶ is COOR. In some embodiments, T⁶ is CHO. In some embodiments, T⁶ is CH₂OH. In some embodiments, T⁶ is OH. In some embodiments, T⁶ is OR. In some embodiments, T⁶ is SH. In some embodiments, T⁶ is SR. In some embodiments, T⁶ is C(O)N(R)₂. In some embodiments, T⁶ is C(O)NHR. In some embodiments, T⁶ is C(O)NH₂. In some embodiments, T⁶ is halide. In some embodiments, T⁶ is tosylate. In some embodiments, T⁶ is mesylate. In some embodiments, T⁶ is SO₂NHR. In some embodiments, T⁶ is triflate. In some embodiments, T⁶ is isocyanate. In some embodiments, T⁶ is cyanate. In some embodiments, T⁶ is thiocyanate. In some embodiments, T⁶ is isothiocyanate. In some embodiments, T⁶ is R. In some embodiments, T⁶ is cyano. In some embodiments, T⁶ is CF₃. In some embodiments, T⁶ is Si(OR)₃.

In some embodiments, R is methyl, ethyl, isopropyl, n-propyl, alkyl, haloalkyl, cycloalkyl, heterocycloalkyl, aryl, or benzyl. In some embodiments, R is methyl. In some embodiments, R is ethyl. In some embodiments, R is isopropyl. In some embodiments, R is n-propyl. In some embodiments, R is alkyl. In some embodiments, R is haloalkyl. In some embodiments, R is cycloalkyl. In some embodiments, R is heterocycloalkyl. In some embodiments, R is aryl. In some embodiments, R is benzyl.

In some embodiments, M¹ is selected from any alkali metal. In some embodiments, M¹ is Li, Na, K, Rb or Cs. In some embodiments, M¹ is Li. In some embodiments, M¹ is Na. In some embodiments, M¹ is K. In some embodiments, M¹ is Rb. In some embodiments, M¹ is Cs.

In some embodiments, M² is selected from any alkaline earth metal. In some embodiments, M¹ is Be, Mg, Ca, Sr, Ba or Ra. In some embodiments, M¹ is Be. In some embodiments, M¹ is Mg. In some embodiments, M¹ is Ca. In some embodiments, M¹ is Sr. In some embodiments, M¹ is Ba. In some embodiments, M¹ is Ra.

An “alkyl” group refers, in some embodiments, to a saturated aliphatic hydrocarbon, including straight-chain or branched-chain. In some embodiments, alkyl is linear or branched. In some embodiments, alkyl is optionally substituted linear or branched. In some embodiments, alkyl is methyl. In some embodiments alkyl is ethyl. In some embodiments, the alkyl group has 1-20 carbons. In some embodiments, the alkyl group has 1-8 carbons. In some embodiments, the alkyl group has 1-7 carbons. In some embodiments, the alkyl group has 1-6 carbons. In some embodiments, non-limiting examples of alkyl groups include methyl, ethyl, isopropyl, n-propyl, isobutyl, butyl, pentyl or hexyl. In some embodiments, the alkyl group has 1-4 carbons. In some embodiments, the alkyl group may be optionally substituted by one or more groups selected from halide, hydroxy, alkoxy, carboxylic acid, aldehyde, carbonyl, amido, cyano, nitro, amino, alkenyl, alkynyl, aryl, azide, epoxide, ester, acyl chloride and thiol.

A “cycloalkyl” group refers, in some embodiments, to a ring structure comprising carbon atoms as ring atoms, which are saturated, substituted or unsubstituted. In some embodiments the cycloalkyl is a 3-12 membered ring. In some embodiments the cycloalkyl is a 6 membered ring. In some embodiments the cycloalkyl is a 5-7 membered ring. In some embodiments the cycloalkyl is a 3-8 membered ring. In some embodiments, the cycloalkyl group may be unsubstituted or substituted by a halogen, alkyl, haloalkyl, hydroxyl, alkoxy, carbonyl, amido, alkylamido, dialkylamido, cyano, nitro, CO₂H, amino, alkylamino, dialkylamino, carboxyl, thio and/or thioalkyl. In some embodiments, the cycloalkyl ring may be fused to another saturated or unsaturated 3-8 membered ring. In some embodiments, the cycloalkyl ring is an unsaturated ring. Non limiting examples of a cycloalkyl group comprise cyclohexyl, cyclohexenyl, cyclopropyl, cyclopropenyl, cyclopentyl, cyclopentenyl, cyclobutyl, cyclobutenyl, cycloctyl, cycloctadienyl (COD), cycloctaene (COE) etc.

A “heterocycloalkyl” group refers in some embodiments, to a ring structure of a cycloalkyl as described herein comprising in addition to carbon atoms, sulfur, oxygen, nitrogen or any combination thereof, as part of the ring. In some embodiments, non-limiting examples of heterocycloalkyl include pyrrolidine, pyrrole, tetrahydrofuran, furan, thiolane, thiophene, imidazole, pyrazole, pyrazolidine, oxazolidine, oxazole, isoxazole, thiazole, isothiazole, thiazolidine, dioxolane, dithiolane, triazole, furazan, oxadiazole, thiadiazole, dithiazole, tetrazole, piperidine, oxane, thiane, pyridine, pyran, thiopyran, piperazine, morpholine, thiomorpholine, dioxane, dithiane, diazine, oxazine, thiazine, dioxine, triazine, and trioxane.

A “crown etheryl” group refers in some embodiments to a cyclic structure that comprises several ether groups. In some embodiments, the cyclic structure comprises a —CH₂CH₂O— repeating unit. In some embodiments, the cyclic structure optionally comprises a —CH₂CH₂NH— repeating unit. In some embodiments, non-limiting examples of the cyclic structure has between 4-10 repeating units. In some embodiments, the cyclic structure is substituted. Substitutions include but are not limited to: F, Cl, Br, I, C₁-C₅ linear or branched alkyl, C₁-C₅ linear or branched haloalkyl, C₁-C₅ linear or branched alkoxy, C₁-C₅ linear or branched haloalkoxy, CF₃, CN, NO₂, —CH₂CN, NH₂, NH-alkyl, N(alkyl)₂, hydroxyl, —OC(O)CF₃, —OCH₂Ph, —NHCO-alkyl, COOH, —C(O)Ph, C(O)O-alkyl, C(O)H, or —C(O)NH₂.

A cyclamyl, cyclenyl, 1,4,7-Triazacyclononanyl, hexacyclenyl, groups refer in some embodiment to cyclic structures that comprise several repeating units that contain alkylamino groups. In some other embodiments, the cyclic structures are substituted. Substitutions include but are not limited to: F, Cl, Br, I, C₁-C₅ linear or branched alkyl, C₁-C₅ linear or branched haloalkyl, C₁-C₅ linear or branched alkoxy, C₁-C₅ linear or branched haloalkoxy, CF₃, CN, NO₂, —CH₂CN, NH₂, NH-alkyl, N(alkyl)₂, hydroxyl, —OC(O)CF₃, —OCH₂Ph, —NHCO-alkyl, COOH, —C(O)Ph, C(O)O-alkyl, C(O)H, or —C(O)NH₂.

A “cryptandyl” group refers in some embodiments to a three dimensional structure that comprises several ether and alkylamino groups. In some embodiments, the structure is a [2.2.2]Cryptand: N[CH₂CH₂OCH₂CH₂OCH₂CH₂]₃N (1,10-diaza-4,7,13,16,21,24-hexaoxabicyclo[8.8.8]hexacosane). In some embodiments, the cyclic structure is substituted. Substitutions include but are not limited to: F, Cl, Br, I, C₁-C₅ linear or branched alkyl, C₁-C₅ linear or branched haloalkyl, C₁-C₅ linear or branched alkoxy, C₁-C₅ linear or branched haloalkoxy, CF₃, CN, NO₂, —CH₂CN, NH₂, NH-alkyl, N(alkyl)₂, hydroxyl, —OC(O)CF₃, —OCH₂Ph, —NHCO-alkyl, COOH, —C(O)Ph, C(O)O-alkyl, C(O)H, or —C(O)NH₂.

As used herein, the term “aryl” refers to any aromatic ring that is directly bonded to another group and can be either substituted or unsubstituted. The aryl group can be a sole substituent, or the aryl group can be a component of a larger substituent, such as in an arylalkyl, arylamino, arylamido, etc. Ex emplary aryl groups include, without limitation, phenyl, tolyl, xylyl, furanyl, naphthyl, pyridinyl, pyrimidinyl, pyridazinyl, pyrazinyl, triazinyl, thiazolyl, oxazolyl, isooxazolyl, pyrazolyl, imidazolyl, thiophene-yl, pyrrolyl, phenylmethyl, phenylethyl, phenylamino, phenylamido, etc. Substitutions include but are not limited to: F, Cl, Br, I, C₁-C₅ linear or branched alkyl, C₁-C₅ linear or branched haloalkyl, C₁-C₅ linear or branched alkoxy, C₁-C₅ linear or branched haloalkoxy, CF₃, CN, NO₂, —CH₂CN, NH₂, NH-alkyl, N(alkyl)₂, hydroxyl, —OC(O)CF₃, —OCH₂Ph, —NHCO-alkyl, COOH, —C(O)Ph, C(O)O-alkyl, C(O)H, or —C(O)NH₂.

In some embodiments, the term “halide” used herein refers to any substituent of the halogen group (group 17). In some embodiments, halide is flouride, chloride, bromide or iodide. In some embodiments, halide is fluoride. In some embodiments, halide is chloride. In some embodiments, halide is bromide. In some embodiments, halide is iodide.

In some embodiments, “haloalkyl” refers to alkyl, alkenyl, alkynyl or cycloalkyl substituted with one or more halide atoms. In some embodiments, haloalkyl is partially halogenated. In some embodiments haloalkyl is perhalogenated (completely halogenated, no C—H bonds). In some embodiments, haloalkyl is CH₂CF₃. In some embodiments. haloalkyl is CH₂CCl₃. In some embodiments, haloalkyl is CH₂CBr₃. In some embodiments, haloalkyl is CH₂CI₃. In some embodiments, haloalkyl is CF₂CF₃. In some embodiments, haloalkyl is CH₂CH₂CF₃. In some embodiments, haloalkyl is CH₂CF₂CF₃. In some embodiments, haloalkyl is CF₂CF₂CF₃. In some embodiments ,the haloalkyl group may be optionally substituted by one or more groups selected from halide, hydroxy, alkoxy, carboxylic acid, aldehyde, carbonyl, amido, cyano, nitro, amino, alkenyl, alkynyl, aryl, azide, epoxide, ester, acyl chloride and thiol.

In some embodiments, the term “benzyl” used herein refers to a methylene (CH₂, CHR or CR₂) connected to an “aryl” (described above) moiety. In some embodiments, the methylene is non substituted (CH₂). In some embodiments, the methylene is substituted (CHR or CR₂). In some embodiments, the methylene is substituted with alkyl, haloalkyl, cycloalkyl, heterocycloalkyl, aryl, benzyl or any combination of such moieties.

In some embodiments, X¹ is S, O or CH₂. In some embodiments, X¹ is S. In some embodiments, X¹ is O. In some embodiments, X¹ is CH₂.

In some embodiments, X² is S, O or CH₂. In some embodiments, X² is S. In some embodiments, X² is O. In some embodiments, X² is CH₂.

In some embodiments, X³ is S, O or CH₂. In some embodiments, X³ is S. In some embodiments, X³ is O. In some embodiments, X³ is CH₂.

In some embodiments, X⁴ is S, O or CH₂. In some embodiments, X⁴ is S. In some embodiments, X⁴ is O. In some embodiments, X⁴ is CH₂.

FIG. 5A is a high level schematic illustration of bonding molecules 116 forming a surface molecules layer 117 on anode 100 and/or anode active material particles 110, according to some embodiments of the invention. It is emphasized that FIG. 5A is highly schematic and represents principles for selecting bonding molecules 116, according to some embodiments of the invention. Actual bonding molecules 116 may be selected according to requirements, e.g., from bonding molecules 116 represented by any one of formulas I-VII, under any of their embodiments.

FIG. 5B is a high level schematic illustration of non-limiting examples for bonding molecules 116, according to some embodiments of the invention. Non-limiting examples for bonding molecules 116 include any of the following: lithium 4-methylbenzenesulfonate, lithium 3,5-dicarboxybenzenesulfonate, lithium sulfate, lithium phosphate, lithium phosphate monobasic, lithium trifluoromethanesulfonate, lithium 4-dodecylbenzenesulfonate, lithium propane-1-sulfonate, lithium 1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-heptadecafluorooctane-1-sulfonate, lithium 2,6-dimethylbenzene-1,4-disulfonate, lithium 2,6-di-tert-butylbenzene-1,4-disulfonate, 3,3′-((1,2-dithiane-4,5-diyl)bis(oxy))bis(N-hydroxypropanamide), 3,3′-((4-mercapto-1,2-phenylene)bis(oxy))bis(N-hydroxypropanamide), lithium aniline sulfonate (the sulfonate may be in any of para, meta and ortho positions) as well as poly(lithium-4-styrenesulfonate) applied in coating the anode material particles. It is noted that in cases of coatings that contain lithium (e.g., metallic lithium), ionic liquid additive(s) 135 may be selected to be not reactive toward it.

For example, various coatings of the anode active material may be used to bond or enhance bonding of molecules 116 to anode material 110, as disclosed above. The size(s) of molecules 116 may be selected to provide good lithium ion conductivity therethrough. In certain embodiments, molecules 116 may be selected (e.g., some of the disclosed salts) to form channels configured to enable fast lithium ion movement therethrough.

Surface molecules layer 117 may be configured to prevent contact of electrolyte solvent (of electrolyte 85) with anode active material 110, e.g., through steric hindrance by molecules 116. Non-limiting examples are embodiments represented e.g., by formulas II, IV and V, among others, such as the non-limiting examples lithium 3,5-dicarboxybenzenesulfonate, lithium 2,6-di-tert-butylbenzene-1,4-disulfonate, 3,3′-((1,2-dithiane -4,5-diyl)bis(oxy))bis(N-hydroxypropanamide), 3,3′-((4-mercapto-1,2-phenylene)bis(oxy))bis(N-hydroxypropanamide), etc.

Molecules 116 may be selected and attached onto anode active material 110 in a way that forms a mechanical and/or electrostatic barrier towards electrolyte solvent and prevents it from reaching and interacting with anode active material 110. Bonding molecules 116 may be selected to have electron rich groups that provide mobile electric charge on the surface of molecules layer 117. Non-limiting examples are embodiments represented e.g., by formulas II, and IV-VII, having conjugated double bonds, acidic groups and benzene groups, among others, such as the non-limiting examples lithium 4-methylbenzenesulfonate, lithium 3,5-dicarboxybenzenesulfonate, lithium 2,6-dimethylbenzene -1,4-disulfonate, 3,3′-((1,2-dithiane-4,5-diyl)bis(oxy))bis(N-hydroxypropanamide), 3,3′-((4-mercapto-1,2-phenylene)bis(oxy))bis(N-hydroxypropanamide), lithium aniline sulfonate, poly(lithium-4-styrenesulfonate) etc.

For example, bonding molecules 116 may be selected to have a width W (anchored in anode 100 and/or anode active material particles 110) of up to three benzene rings and a length L (protruding into electrolyte 105) of up to four benzene rings, as exemplified in a non-limiting manner in embodiments represented e.g., by formulas II and VII having bicyclic or tricyclic structures, e.g., anthracene-based structures and/or in embodiments represented e.g., by formulas IV and V.

In some embodiments, bonding molecules 116 may comprise an anode material anchoring part 116A, configured to bind to or be associated with anode active material 110, e.g., via lithium, thiols, or other functional groups in bonding molecules 116. In some embodiments, anode material anchoring part 116A may be pre-lithiated exemplified in a non-limiting manner in embodiments represented by any of formulas I-VII which include lithium, such as the non-limiting examples illustrated in FIG. 5B.

In some embodiments, bonding molecules 116 may comprise an ionic conductive part 116B having an ionic conductivity which is much higher than its electronic conductivity, e.g., by one, two, three or more orders of magnitude. Ionic conductive part 116B may extend through most or all of length L of bonding molecules 116 and provide a conductivity path 91A (illustrated schematically) for lithium ions 91 moving back and forth between electrolyte 105 and anode 110 during charging and discharging cycles. Conductivity paths 91A may be provided e.g., by conjugated double bonds, acidic groups, benzene rings, carbon-fluorine bonds, charged functional groups etc. which are disclosed above. For example, the charge distribution on bonding molecules 116 may be selected to be mobile and support lithium ion movement across molecules layer 117, possibly reducing the charge of the lithium ion to Li^(δ+) as explained above, to prevent metallization on the surface of anode 110. Partial charge reduction may be carried out by electron rich groups such as aromatic groups and acidic groups disclosed above.

In some embodiments, bonding molecules 116 may comprise a top, ionic liquid binding part 116C configured to bind cations 132 and/or anions 131 of ionic liquid additive 135 in electrolyte 105. For example, embodiments represented by any of formulas I-VII which involve charged and/or polar functional groups may provide top, ionic liquid binding part 116C, e.g., lithium 3,5-dicarboxybenzenesulfonate, lithium sulfate, lithium phosphate, lithium phosphate monobasic, lithium trifluoromethanesulfonate, lithium 1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-heptadecafluorooctane -1-sulfonate, lithium 2,6-dimethylbenzene-1,4-disulfonate, lithium 2,6-di-tert-butylbenzene-1,4-disulfonate, 3,3′-((1,2-dithiane-4,5-diyl)bis(oxy))bis(N-hydroxypropanamide), 3,3′-((4-mercapto-1,2-phenylene)bis(oxy))bis(N-hydroxypropanamide), lithium aniline sulfonate (the sulfonate may be in any of para, meta and ortho positions) as well as poly(lithium-4-styrenesulfonate), as some non-limiting examples. Ionic liquid binding part 116C may be further configured to stabilize electrolyte-buffering zone(s) 130 as described above.

FIG. 6 is a high level schematic illustration of bonding molecules 116 forming surface molecules layer 117 on anode 100 and/or anode active material particles 110, according to some embodiments of the invention. In the illustrated non-limiting example, bonding molecules 116 comprise a combination of lithium borates 102A which anchor (116A) layer 117 to anode active material 110, and polymer molecules (116B) having electron rich groups (e.g., conjugated bonds, acidic groups, etc.) which provide, together with lithium borates interconnecting the polymer molecules, ionic conductivity paths 91A through layer 117 and have an ionic conductivity which is much larger than electronic conductivity (e.g., by one or few orders of magnitude). Either or both the lithium borate molecules and the polymer molecules may have electron rich groups and may be pre-lithiated. Surface molecules layer 117 may comprise multiple polymer layers interconnected by lithium borates. Surface molecules layer 117 may bond cations 132 and/or anions 131 of ionic liquid (additive) at its top layer 116C, yet may also operate with prior art electrolyte 85 due to its efficient blocking of contact between the solvent of electrolyte 85 and anode active material 110. It is noted that lithium borates and lithium phosphates 102A may likewise be used similarly to Li₂B₄O₇, which is provided in FIG. 6 as a non-limiting example.

FIG. 7 is a high level schematic illustration of bonding molecules 116 forming thick surface molecules layer 117 on anode 100 and/or anode active material particles 110, according to some embodiments of the invention. In certain embodiments, bonding molecules 116 may extend deep into electrolyte 105 to form thick surface molecules layer 117 having a length L of more than ten benzene rings. For example, surface layer 117 may be thick to an extent of 10% or more of the distance between anode 100 and separator 86. The charge distribution on bonding molecules 116 in ionic conductive part 116B may be selected to be mobile and support lithium ion movement across molecules layer 117, possibly reducing the charge of the lithium ion to Li^(δ+) as explained above, to prevent metallization on the surface of anode 110. Partial charge reduction may be carried out by electron rich groups such as aromatic groups and acidic groups disclosed above. Certain embodiments comprise surface molecules layer 117 having intermediate thickness of between 4-10 benzene rings.

FIGS. 8A and 8B are high level schematic illustrations of a lithium ion cell 150 with electrolyte 105 during charging, according to some embodiments of the invention. Lithium ion cell 150 comprises a metalloid anode 100, comprising at least one of C, graphite, Si, Sn, Ge and Al, and electrolyte 105 comprising at most 20% of at least one ionic liquid as ionic liquid additive 135. Ionic liquid additive 135 may form a mobile SEI (e.g., in place of the (static) SEI, in addition to the SEI or in an interaction with the SEI) on anode 100, e.g., during charging, as illustrated in FIG. 8A and disclosed above.

In certain embodiments, electrolyte 105 may comprise at most 5% of the at least one ionic liquid. In certain embodiments, the at least one ionic liquid may comprise sulfonylimides-piperidinium derivatives ionic liquid(s). Ionic liquid additive 135 may be selected to have a melting temperature below 10° C., below 0° C. or below −4° C., in certain embodiments.

Layer 145 may be part of the anode surface or coated thereupon, and bind at least a part of ionic liquid additive 135 to hold at least stationary portion 140A of ionic liquid additive 135 at the anode surface to support the SEI, prevent decomposition of electrolyte 105 and prevent lithium metallization on anode 100. Layer 145 of bonding molecules 116 and/or layer 140A of bonded ionic liquid additive may also provide some negative electric charge that partly reduces the lithium ion, leaving them with a partial charge δ⁺ and preventing full reduction and metallization of lithium on the anode surface. Layer 145 of bonding molecules 116 and/or layer 140A of bonded ionic liquid additive may be configured to support gradient 120 described in FIG. 3A.

FIG. 9 is a high level flowchart illustrating a method 200, according to some embodiments of the invention. The method stages may be carried out with respect to cells 150 described above and lithium ion batteries constructed therefrom, which may optionally be configured to implement method 200. Method 200 may comprise stages for producing, preparing and/or using cells 150, such as any of the following stages, irrespective of their order.

Method 200 may comprise adding up to 20% of at least one ionic liquid to an electrolyte used in lithium ion batteries (stage 210), using metalloid-based anodes (stage 215), e.g., comprising at least one of C, graphite, Si, Sn, Ge and Al, and using the electrolyte with the ionic liquid additive to prevent lithium metallization in lithium ion batteries (stage 220). Method 200 may comprise selecting one or more ionic liquids to have cations and/or anions which are much larger than lithium ions, e.g., two to ten times the size (e.g., volume) thereof (stage 212). In certain embodiments, electrolyte 105 may comprise at most 5% of the at least one ionic liquid. In certain embodiments, the at least one ionic liquid may comprise sulfonylimides-piperidinium derivatives ionic liquid(s). Ionic liquid additive 135 may be selected to have a melting temperature below 10° C., below 0° C. or below −4° C.

In certain embodiments, method 200 may comprise forming a surface layer on the anode to bond (e.g., electrostatically and/or ionically) at least some of the ionic liquid additive(s) (stage 230), e.g., by coating the anode active material by various bonding molecules as disclosed above and/or partly or fully pre-coating and/or coating the active material using corresponding polymers (stage 235).

Method 200 may comprise carrying out the bonding during at least a first charging cycle of the cell (stage 240), possibly during several first charging and discharging cycles. In certain embodiments, the bonding of cations and/or anions may be carried out, at least partially, on the active material itself, even before the first charging cycle. The bonding of the ionic liquid to the bonding layer may be electrostatic and/or salt-like (ionic). In certain embodiments, the bonding may be at least partly covalent.

Method 200 may comprise stabilizing the SEI of the cell through the bonded portion of the ionic liquid additive(s) to the surface layer (stage 250).

Method 200 may further comprise configuring the bonding molecules to prevent contact of electrolyte solvent with anode active material, e.g., through steric hindrance (stage 260).

Method 200 may further comprise configuring the bonding molecules to have electron rich groups that provide mobile electric charge on the surface of molecules layer (stage 270), e.g., to provide an ionic conductivity path through the surface molecules layer (stage 275).

Method 200 may further comprise pre-lithiating the anode active material through an anode material anchoring part of the bonding molecules (stage 280).

Method 200 may comprise using anchored and interconnected conductive polymer molecules as the surface layer (stage 290). Alternatively or complementarily, method 200 may comprise using a thick surface layer that protrude significantly into the electrolyte (stage 295).

FIGS. 10A and 10B are non-limiting examples which indicate reversible lithiation at the anode when using the ionic liquid additive according to some embodiments of the invention (FIG. 10A) with respect to the prior art (FIG. 10B). Charging and discharging cycles at 1 C (ca. 1 hour charging followed by 1 hour discharging) are shown for half-cells having anodes 100 operate with lithium as cathodes 87—in FIG. 10A with ionic liquid additive 135 being N,N-Diethyl-N-methyl-N-propylammonium (cation 132) and bis(fluorosulfonyl)imide (anion 131) (electrolyte 105, with 1% ionic liquid additive 135) and in FIG. 10B without ionic liquid additive 135 (electrolyte 85—FEC:DMC (3:7) and 2% VC). The cycles were performed after four formation cycles at 0.03 C (discharge to 80% of the capacity) followed by one cycle at 0.1 C, limited by capacity. Without being bound by theory, the continuous rise in the discharge voltage from cycle to cycle (while the capacity during charging and discharging remains constant at ca. 600 mAh/gr) in FIG. 10A (in contrast to FIG. 10B) is understood as indicating the reversibility of lithium excess in the anode (e.g., lithiated lithium during the first slow cycles) facilitated through the ionic liquid additive preventing the lithium ions from binding to the anode active material permanently and/or possibly contributing to formation of a relatively lithium poor SEI.

In the above description, an embodiment is an example or implementation of the invention. The various appearances of “one embodiment”, “an embodiment”, “certain embodiments” or “some embodiments” do not necessarily all refer to the same embodiments. Although various features of the invention may be described in the context of a single embodiment, the features may also be provided separately or in any suitable combination. Conversely, although the invention may be described herein in the context of separate embodiments for clarity, the invention may also be implemented in a single embodiment. Certain embodiments of the invention may include features from different embodiments disclosed above, and certain embodiments may incorporate elements from other embodiments disclosed above. The disclosure of elements of the invention in the context of a specific embodiment is not to be taken as limiting their use in the specific embodiment alone. Furthermore, it is to be understood that the invention can be carried out or practiced in various ways and that the invention can be implemented in certain embodiments other than the ones outlined in the description above.

The invention is not limited to those diagrams or to the corresponding descriptions. For example, flow need not move through each illustrated box or state, or in exactly the same order as illustrated and described. Meanings of technical and scientific terms used herein are to be commonly understood as by one of ordinary skill in the art to which the invention belongs, unless otherwise defined. While the invention has been described with respect to a limited number of embodiments, these should not be construed as limitations on the scope of the invention, but rather as exemplifications of some of the preferred embodiments. Other possible variations, modifications, and applications are also within the scope of the invention. Accordingly, the scope of the invention should not be limited by what has thus far been described, but by the appended claims and their legal equivalents. 

We claim:
 1. A lithium ion cell comprising at least one anode comprising at least one of: Si, Ge, Sn and LTO anode material particles, at least one cathode, a liquid carbonate-based electrolyte, and an additive to the electrolyte, which is at most 5% by volume of the electrolyte, the additive comprising an ionic liquid consisting of sulfonylimide-derived anions and piperidinium-derived cations and is liquid at room temperature or below, wherein the at least one anode is made of surface-coated anode material particles having surface layers of bonding molecules around the particles, which are attached to the anode material particles prior to using the surface-coated anode material particles for a formation of the at least one anode, wherein the bonding molecules have a width W, anchored in the anode active material particles, of up to three benzene rings and a length L, protruding into the electrolyte, of up to four benzene rings, wherein the bonding molecules are configured to bond at least a portion of the piperidinium-derived cations upon charging of the lithium ion cell, and wherein the bonding molecules are selected from the group consisting of lithium 4-methylbenzenesulfonate, lithium 3,5-dicarboxybenzenesulfonate, lithium 4-dodecylbenzenesulfonate, lithium 2,6-dimethylbenzene-1,4-disulfonate, lithium 2,6-di-tert-butylbenzene-1,4-disulfonate, lithium aniline sulfonate, and combinations thereof, wherein the bonding molecules are bonded to the anode material particles at a sulfonate group thereof. 